WO2017093348A1 - Microbiocidal oxadiazole derivatives - Google Patents

Microbiocidal oxadiazole derivatives Download PDF

Info

Publication number
WO2017093348A1
WO2017093348A1 PCT/EP2016/079329 EP2016079329W WO2017093348A1 WO 2017093348 A1 WO2017093348 A1 WO 2017093348A1 EP 2016079329 W EP2016079329 W EP 2016079329W WO 2017093348 A1 WO2017093348 A1 WO 2017093348A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogen
methyl
formula
compound
compounds
Prior art date
Application number
PCT/EP2016/079329
Other languages
French (fr)
Inventor
Thomas James HOFFMAN
Daniel Stierli
Martin Pouliot
Renaud Beaudegnies
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 CN201680070488.2A priority Critical patent/CN108289448B/en
Priority to JP2018528660A priority patent/JP6930972B2/en
Priority to BR112018011053A priority patent/BR112018011053A2/en
Priority to EP16802115.2A priority patent/EP3383179B1/en
Priority to ES16802115T priority patent/ES2810752T3/en
Priority to DK16802115.2T priority patent/DK3383179T3/en
Priority to US15/780,007 priority patent/US10640497B2/en
Priority to SI201630875T priority patent/SI3383179T1/en
Application filed by Syngenta Participations Ag filed Critical Syngenta Participations Ag
Priority to MX2018006474A priority patent/MX2018006474A/en
Priority to PL16802115T priority patent/PL3383179T3/en
Publication of WO2017093348A1 publication Critical patent/WO2017093348A1/en
Priority to ZA2018/02969A priority patent/ZA201802969B/en
Priority to IL259695A priority patent/IL259695B/en
Priority to CONC2018/0005793A priority patent/CO2018005793A2/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—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 carbon chain containing aromatic rings
    • 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
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • 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
    • C07D417/10—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 carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/08—Bridged systems

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.
  • n 0 or 1 or 2;
  • a 1 represents N or CR ⁇ wherein R represents hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy;
  • a 2 represents N or CR 2 , wherein R 2 represents hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy;
  • a 3 represents N or CR 3 , wherein R 3 represents hydrogen or halogen
  • a 4 represents N or CR 4 , wherein R 4 represents hydrogen or halogen; and wherein no more than two of A 1 to A 4 are N;
  • R 5 and R 6 independently represent hydrogen, halogen, cyano, difluoromethyl, trifluoromethyl, or Ci-4alkyl, or together with the carbon atom to which they are bonded represent cyclopropyl;
  • Z represents a roup selected from Z-1 , Z-2, Z-3 or Z-4:
  • B and B 2 in Z-1 represent C(R 7 )(R 8 ); or
  • Z represents a group selected from Z-6, wherein Z-6 represents Z-6a, Z-6b, Z-6c or Z-6d:
  • R 7 and R 8 independently represent hydrogen, halogen, Ci C4alkyl, Ci C4haloalkyl or Ci- C4alkoxy;
  • R 9 represents hydrogen, d ealkyl, Cs ealkenyl, Cs ealkynyl, C3-6cycloalkyl, d ealkoxy, C(0)R 10 ,
  • Ci- 6 alkyl, C 3 - 6 alkenyl, C 3 - 6 alkynyl, C 3 - 6cycloalkyl and d ealkoxy are optionally substituted by halogen or cyano;
  • R 0 represents hydrogen, d ealkyl, d ecycloalkyl, d-6cycloalkyld-2alkyl, d-4alkoxyd-4alkyl, wherein d ealkyl, d ecycloalkyl, d-6cycloalkyld-2alkyl and d-4alkoxyd-4alkyl are optionally substituted by halogen or cyano; and
  • R represents hydrogen, d-4alkyl, d-4haloalkyl, d-4alkoxy or d-4alkoxy-d-4alkyl; or a salt or an N-oxide thereof.
  • an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I).
  • a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms wherein a fungicidally effective amount of a compound of formula (I), or a composition comprising this compound as active ingredient, is applied to the plants, to parts thereof or the locus thereof.
  • a compound of formula (I) as a fungicide.
  • the use may exclude methods for the treatment of the human or animal body by surgery or therapy.
  • halogen refers to fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
  • cyano means a -CN group.
  • Ci-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 "Ci-4alkyl” and “Ci-2alkyl” are to be construed accordingly.
  • Examples of d ealkyl include, but are not limited to, methyl, ethyl, n-propyl, 1-methylethyl (iso-propyl), n-butyl,1-dimethylethyl (i-butyl) and n-pentyl.
  • Ci- 4alkylene refers to a corresponding definition of Ci-C4alkyl, except that such radical is attached to the rest of the molecule by two single bonds.
  • the term “C2-4alkylene” is to be construed accordingly.
  • Examples of Ci C4alkylene include, but are not limited to, -CH2-, -CH2CH2- and -(CH2)3-.
  • Cs ealkenyl refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one double bond that can be of either the (E)- or (Z)-configu ration, having from three to six carbon atoms, which is attached to the rest of the molecule by a single bond .
  • Examples of Cs ealkenyl include, but are not limited to, prop- 1-enyl, but-1-enyl.
  • Cs ealkynyl refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having from three to six carbon atoms, and which is attached to the rest of the molecule by a single bond.
  • Examples of Cs ealkynyl include, but are not limited to, prop-1-ynyl, but-1-ynyl.
  • Ci ealkoxy refers to a radical of the formula -OR a where R a is a C1-6 alkyl radical as generally defined above.
  • C1-C4 alkoxy is to be construed accordingly. Examples of d ealkoxy include, but are not limited to, methoxy, ethoxy, propoxy, iso-propoxy, butoxy.
  • Ci-4haloalkyl refers to a Ci-4alkyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • Examples of Ci-4haloalkyl include, but are not limited to fluoromethyl, difluoromethyl, fluoroethyl, trifluoromethyl, 2,2,2-trifluoroethyl.
  • C3-6cycloalkyl refers to a monocyclic radical and contains 3 to 6 carbon atoms. Examples of C3-6cycloalkyl include, but are not limited to, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • C3-6cycloalkylCi-2alkyl refers to a C3-6cycloalkyl ring as defined above attached to the rest of the molecule by a Ci-2alkylene radical as defined above.
  • C3- 6cycloalkylCi-2alkyl examples include, but are not limited to cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclopentylmethyl and cyclohexylmethyl.
  • Ci-4alkoxyCi-4alkyl refers to a Ci-4alkyl radical as generally defined above substituted by a Ci-4alkoxy group as defined above.
  • Examples of Ci-4alkoxyCi-4alkyl include, but are not limited to methoxymethyl, 2-methoxyethyl.
  • 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 is 0 or 1 or 2. In one embodiment of the invention, n is 1. In another embodiment of the invention, n is 0. In a further embodiment of the invention, n is 2.
  • X represents C(O) or S(0)2. In one embodiment of the invention, X is C(O). In another embodiment of the invention, X is S(0)2.
  • a 1 represents N or CR ⁇ wherein R represents hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy.
  • a 1 is CR .
  • R represents hydrogen, halogen, methyl, trifluoromethyl or methoxy. More preferably, R represents hydrogen, halogen or methyl. Even more preferably, R represents hydrogen or fluoro. Most preferably, R represents hydrogen.
  • a 1 is N.
  • a 2 represents N or CR 2 , wherein R 2 represents hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy.
  • a 2 is CR 2 .
  • R 2 represents hydrogen, halogen, methyl, trifluoromethyl or methoxy. More preferably, R 2 represents hydrogen or methyl.
  • a 2 is N.
  • a 3 represents N or CR 3 , wherein R 3 represents hydrogen or halogen. In one embodiment of the invention, A 3 represents CR 3 . Preferably, R 3 represents hydrogen.
  • a 4 represents N or CR 4 , wherein R 4 represents hydrogen or halogen. In one embodiment of the invention, A 4 represents CR 4 . Preferably, R 4 represents hydrogen. In the compounds of Formula (I) according to the invention, no more than two of A 1 to A 4 are
  • N in particular, at least two of R to R 4 may be hydrogen.
  • at least R 2 , R 3 and R 4 are hydrogen.
  • a 1 is CR 1 and R is hydrogen, and A 2 is CR 2 and R 2 is hydrogen;
  • a 1 is CR 1 and R is halogen, and A 2 is CR 2 and R 2 is hydrogen; or
  • a 1 is N and A 2 is CR 2 and R 2 is hydrogen.
  • a 3 is CR 3 and R 3 is hydrogen
  • a 4 is CR 4 and R 4 is hydrogen.
  • the 6-membered ring comprising A 1 to A 4 is a phenyl (where A 1 , A 2 , A 3 and A 4 are C-H), a pyridinyl (where A 1 is N and A 2 , A 3 and A 4 are C-H, or A 3 is N and A 1 , A 2 and A 4 are C-H), a fluorophenyl (where A 1 is C-F and A 2 , A 3 and A 4 are C-H, or A 3 is C-F and A 1 , A 2 and A 4 are C-H) or a difluorophenyl (eg, where A 1 and A 2 are C-F and A 3 and A 4 are C-H, or A 1 and A 3 are C-F and A 2 and A 4 are C-H) group.
  • R 5 and R 6 independently represent hydrogen, halogen, cyano, difluoromethyl, trifluoromethyl, or Ci-4alkyl, or together with the carbon atom to which they are bonded represent cyclopropyl.
  • R 5 and R 6 are hydrogen, or R 5 is hydrogen and R 6 is methyl, or R 5 and R 6 are methyl. Most preferably, R 5 and R 6 are hydrogen.
  • Z represents a group selected from Z-1 , Z-2, Z-3, Z-4, Z-5 (Z-5a, Z-5b, Z-5c, Z-5d, Z-5e, Z-5f, Z- 5g) or Z-6 (Z-6a, Z-6b, Z-6c, Z-6d) as defined herein.
  • Z represents Z-1 , Z-2 or Z-3, and, in particular Z-2 or Z-3. More preferably, Z represents Z-1 , Z-2 or Z-3 when X is C(O), and, in particular Z represents Z-2 or Z-3, when X is C(O).
  • Z represents:
  • Z represents:
  • Z represents:
  • Z represents:
  • Z is Z-2 wherein B , B 2 and B 3 independently represent C(R 7 )(R 8 ) or O, wherein only one of B ⁇ B 2 and B 3 may be O; or Z-3 wherein B , B 2 , B 3 and B 4 independently represent C(R 7 )(R 8 ) or O, wherein only one of B ⁇ B 2 , B 3 and B 4 may be O.
  • Preferred Z groups include:
  • R 7 and R 8 independently represent hydrogen, halogen, Ci C4alkyl, Ci C4haloalkyl or Ci- C4alkoxy.
  • R 7 and R 8 independently represent hydrogen, fluoro, chloro, methyl, ethyl, difluormethyl, trifluoromethyl or methoxy. More preferably, R 7 and R 8 independently represent hydrogen, methyl, difluoromethyl, trifluoromethyl or methoxy. Even more preferably, R 7 is hydrogen or methyl, and R 8 represents hydrogen, methyl, difluoromethyl, trifluoromethyl or methoxy. Still more preferably, R 7 and R 8 independently represent hydrogen or methyl.
  • R 9 represents hydrogen, Ci-ealkyl, Cs ealkenyl, Cs ealkynyl, Cs ecycloalkyl, Ci ealkoxy, C(0)R 10 , C(0)OR 10 , C(O)N(R 0 )R 11 , S(0) 2 Rio or S(0) 2 N(Rio)Rn, wherein Ci-ealkyl, C 3 - 6 alkenyl, C 3 - 6 alkynyl, C 3 - 6cycloalkyl and Ci ealkoxy are optionally substituted by halogen or cyano.
  • R 9 represents hydrogen, Ci-ealkyl, Cs-ealkenyl, Cs-ealkynyl, Cs-ecycloalkyl, Ci-ealkoxy, C(0)R 10 , C(0)OR ° or C(O)N(R 0 )R 11 , wherein Ci-6alkyl, Cs ealkenyl, Cs ealkynyl, C3-6cycloalkyl and Ci ealkoxy are optionally substituted by halogen or cyano.
  • R 9 represents hydrogen, Ci-4alkyl, Ci-4alkoxy, C(0)R 10 , C(0)OR 10 , C(O)N(R 0 )R 11 , S(0) 2 Rio or S(0) 2 N(Rio)Rn. Even more preferably, R 9 represents hydrogen, Ci- 4 alkyl, C(0)R 10 , C(0)OR ° or C(O)N(R 0 )R 11 .
  • R 0 represents hydrogen, Ci-ealkyl, C3-6cycloalkyl, C3-6cycloalkylCi- 2 alkyl, Ci-4alkoxyCi-4alkyl, wherein Ci-ealkyl, Cs ecycloalkyl, C3-6cycloalkyl-Ci- 2 alkyl and Ci-4alkoxy-Ci-4alkyl are optionally substituted by halogen or cyano.
  • R 0 represents hydrogen, Ci-4alkyl or Ci-4alkoxyCi-4alkyl.
  • R represents hydrogen, Ci-4alkyl, Ci-4haloalkyl, Ci-4alkoxy or Ci-4alkoxyCi-4alkyl. Preferably, R represents hydrogen or Ci-4alkyl.
  • R represents hydrogen, Ci-4alkyl, Ci-4haloalkyl, Ci-4alkoxy or Ci-4alkoxyCi-4alkyl.
  • R represents hydrogen or Ci-4alkyl.
  • a 1 is N or CR ⁇ wherein R is hydrogen or halogen
  • a 2 is CR 2 and R 2 is hydrogen;
  • a 3 is CR 3 and R 3 is hydrogen; and
  • a 4 is CR 4 and R 4 is hydrogen;
  • n is 0 or 1 ;
  • R 5 and R 6 are hydrogen, or R 5 is hydrogen and R 6 is methyl, or R 5 and R 6 are methyl;
  • X is C(O) or S(0) 2 ;
  • R 7 and R 8 independently represent hydrogen, methyl, difluoromethyl, trifluoromethyl or methoxy;
  • R 9 represents hydrogen, Ci- 4 alkyl, C(0)R 10 , C(0)OR ° or C(O)N(R 0 )R 11 .
  • R 0 represents hydrogen, Ci-4alkyl or Ci-4alkoxyCi-4alkyl
  • R represents hydrogen or Ci-4alkyl. More preferably, A 1 represents CR and R is hydrogen; A 2 is CR 2 and R 2 is hydrogen; A 3 is CR 3 and R 3 is hydrogen; and A 4 is CR 4 and R 4 is hydrogen;
  • n 1 ;
  • R 5 and R 6 are hydrogen
  • X is C(O);
  • R 7 and R 8 independently represent hydrogen, methyl, difluoromethyl, trifluoromethyl or methoxy
  • R 9 represents hydrogen, Ci- 4 alkyl, C(0)R 10 , C(0)OR ° or C(O)N(R 0 )R 11 ;
  • R 0 represents hydrogen, Ci-4alkyl or Ci-4alkoxyCi-4alkyl
  • R represents hydrogen or Ci-4alkyl.
  • a 1 represents N or CR 1 , wherein R is selected from hydrogen or fluoro;
  • a 2 is CR 2 and R 2 is hydrogen;
  • a 3 is CR 3 and R 3 is hydrogen; and
  • a 4 is CR 4 and R 4 is hydrogen;
  • n 1 ;
  • R 5 and R 6 are hydrogen, or R 5 is hydrogen and R 6 is methyl, or R 5 and R 6 are methyl;
  • Z when X is C(O) represents Z-1 , Z-2, Z-3, Z-5a or Z-5c, or
  • R 7 and R 8 independently represent hydrogen, chloro, fluoro, methyl, ethyl, difluormethyl, trifluoromethyl or methoxy.
  • a 1 represents N or CR 1 , wherein R is selected from hydrogen or fluoro;
  • a 2 is CR 2 and R 2 is hydrogen;
  • a 3 is CR 3 and R 3 is hydrogen; and
  • a 4 is CR 4 and R 4 is hydrogen;
  • n 1 ;
  • R 5 and R 6 are hydrogen, or R 5 is hydrogen and R 6 is methyl, or R 5 and R 6 are methyl;
  • X is C(O);
  • Z represents Z-1 , Z-2, Z-3, Z-6a or Z-6c;
  • R 7 and R 8 independently represent hydrogen, chloro, fluoro, methyl, ethyl, difluormethyl, trifluoromethyl or methoxy. Even more preferably, A 1 represents N or CR 1 , wherein R is hydrogen; A 2 is CR 2 and R 2 is hydrogen, A 3 is CR 3 and R 3 is hydrogen, and A 4 is CR 4 and R 4 is hydrogen;
  • n 1 ;
  • R 5 and R 6 are hydrogen
  • X is C(O);
  • R 7 and R 8 independently represent hydrogen, methyl, difluoromethyl, trifluoromethyl or methoxy.
  • a 1 represents CR 1 and R is hydrogen
  • a 2 is CR 2 and R 2 is hydrogen
  • a 3 is CR 3 and R 3 is hydrogen
  • a 4 is CR 4 and R 4 is hydrogen
  • n 1 ;
  • R 5 and R 6 are hydrogen
  • X is C(O);
  • Z represents Z-2 wherein B , B 2 and B 3 independently represent C(R 7 )(R 8 ) or O, wherein only one of B , B 2 and B 3 may be O, or Z-3 wherein B , B 2 , B 3 and B 4 independently represent C(R 7 )(R 8 ) or O, wherein only one of B ⁇ B 2 , B 3 and B 4 may be O; and
  • R 7 and R 8 independently represent hydrogen or methyl.
  • a 1 represents CR 1 and R is hydrogen
  • a 2 is CR 2 and R 2 is hydrogen
  • a 3 is CR 3 and R 3 is hydrogen
  • a 4 is CR 4 and R 4 is hydrogen
  • n 1 ;
  • R 5 and R 6 are hydrogen
  • X is C(O);
  • Z represents Z-2 wherein B , B 2 and B 3 independently represent C(R 7 )(R 8 ), or Z-3 wherein B , B 2 , B 3 and B 4 independently represent C(R 7 )(R 8 );
  • R 7 and R 8 independently represent hydrogen or methyl.
  • a 1 is N or CR 1 wherein R is hydrogen or fluorine, A 2 is CR 2 and R 2 is hydrogen, A 3 is N or CR 3 and R 3 is hydrogen or fluorine, and A 4 is CR 4 and R 4 is hydrogen;
  • n 1 ;
  • R 5 and R 6 are hydrogen, or R 5 is hydrogen and R 6 is methyl, or R 5 and R 6 are methyl;
  • X is C(O);
  • B and B 2 are C(R 7 )(R 8 ) and wherein R 7 is hydrogen and R 8 is hydrogen, methyl, ethyl, difluoromethyl, trifluoromethyl or methoxy;
  • B is selected from C(R 7 )(R 8 ) and wherein R 7 and R 8 are independently selected from hydrogen and Ci-4alkyl, or NR 9 wherein R 9 is selected from hydrogen or Ci-4alkyl;
  • B 2 is selected from C(R 7 )(R 8 ) wherein R 7 and R 8 are independently selected from hydrogen and Ci-4alkyl, or NR 9 _
  • R 9 is selected from C(O)N(R 0 )R 11 or S(O) 2 N(R 0 )R ⁇ wherein R 0 is selected from hydrogen, or methyl and R is selected from hydrogen, methyl or methoxy;
  • B 3 is C(R 7 )(R 8 ) wherein R 7 and R 8 are independently selected from hydrogen and Ci-4alkyl; and
  • R 7 and R 8 are independently selected from hydrogen and Ci- 4alkyl
  • a 1 is CR and R is hydrogen
  • a 2 is CR 2 and R 2 is hydrogen
  • a 3 is CR 3 and R 3 is hydrogen
  • a 4 is CR 4 and R 4 is hydrogen
  • n 1 ;
  • R 5 and R 6 are hydrogen
  • X is C(O);
  • B and B 2 are C(R 7 )(R 8 ) and wherein R 7 is hydrogen and R 8 is hydrogen, methyl, difluoromethyl, trifluoromethyl or methoxy;
  • B is C(R 7 )(R 8 ) wherein R 7 and R 8 are independently selected from hydrogen and methyl
  • B 2 is C(R 7 )(R 8 ) wherein R 7 and R 8 are independently selected from hydrogen and methyl
  • B is selected from C(R 7 )(R 8 ) and wherein R 7 and R 8 are independently selected from hydrogen and methyl, or NR 9 wherein R 9 is selected from hydrogen or Ci-4alkyl
  • B 2 is selected from C(R 7 )(R 8 ) wherein R 7 and R 8 are independently selected from hydrogen and methyl, or NR 9 wherein R 9 is selected from C(O)N(R 0 )R 11 or S(O) 2 N(R 0 )R ⁇ wherein R 0 is selected from hydrogen or methyl and R is selected from hydrogen, methyl or methoxy
  • B 3 is C(R 7 )(R 8 ) wherein R 7 and R 8 are independently selected from hydrogen and methyl
  • Z-5c wherein a is 0, and R 7 and R 8 are independently selected from hydrogen and methyl; Z-5g wherein a is 0, and R 7 and R 8 are independently selected from hydrogen and methyl; or Z-6c wherein Y is C2-3alkylene, and R 7 and R 8 are independently selected from hydrogen and methyl.
  • a 1 is CR 1 and R is hydrogen
  • a 2 is CR 2 and R 2 is hydrogen
  • a 3 is CR 3 and R 3 is hydrogen
  • a 4 is CR 4 and R 4 is hydrogen
  • n 1 ;
  • R 5 and R 6 are hydrogen
  • B and B 2 are C(R 7 )(R 8 ) and wherein R 7 is hydrogen and R 8 is hydrogen, methyl, difluoromethyl or trifluoromethyl;
  • B is C(R 7 )(R 8 ) wherein R 7 and R 8 are independently selected from hydrogen and methyl
  • B 2 is C(R 7 )(R 8 ) wherein R 7 and R 8 are independently selected from hydrogen and methyl
  • B is selected from C(R 7 )(R 8 ) and wherein R 7 and R 8 are independently selected from hydrogen and methyl, or NR 9 wherein R 9 is selected from hydrogen or methyl;
  • B 2 is selected from C(R 7 )(R 8 ) wherein R 7 and R 8 are independently selected from hydrogen and methyl, or NR 9 wherein R 9 is selected from C(O)N(R 0 )R 11 or S(O) 2 N(R 0 )R ⁇ wherein R 0 is selected from hydrogen or methyl and R is selected from hydrogen, methyl or methoxy;
  • B 3 is C(R 7 )(R 8 ) wherein R 7 and R 8 are independently selected from hydrogen and methyl; and
  • the compound according to Formula (I) is selected from a compound A-1 to A-70 described in Table A (below), a compound B-1 to B-4 described in Table B (below), a compound C-1 to C-3 described in Table C (below), or compound D-1 described in Table D (below).
  • the compounds of the present invention may be enantiomers of the compound of Formula (I) as represented b a Formula (l-a) or a Formula (l-b), wherein n is 1 , and 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 CF3-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 , Z (X, Y, a, B ⁇ B 2 , B 3 , B 4 , B 5 ), R ⁇ R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 0 and R
  • R ⁇ R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 0 and R 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 , Z (X, Y, a, B ⁇ B 2 , B 3 , B 4 , B 5 ), R ⁇ R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 0 and R as represented in Tables 1 a to 1d below
  • compounds of formula (I), or compounds of formula (XII), can be prepared from compounds of formula (IV) or (IVa), respectively, by treatment with trifluoroacetic anhydride in the presence of a base (e.g. pyridine or 4-dimethylaminopyridine) in a suitable solvent, such as tetrahydrofuran or ethanol, at a temperature between 25°C and 75°C.
  • a base e.g. pyridine or 4-dimethylaminopyridine
  • suitable solvent such as tetrahydrofuran or ethanol
  • Compounds of formula (IV) and (IVa) can be prepared from compounds of formula (V) and (Va), respectively, by treating them 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 65°C.
  • a base such as triethylamine
  • a suitable solvent such as methanol
  • Compounds of formula (V) and (Va) can be prepared from compounds of formula (VI) and (Via), respectively, wherein V 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 (e.g. dimethylformamide or N-methylpyrrolidone) at elevated temperature between 100°C and 120°C.
  • a suitable cyanide reagent such as Pd(0)/Zn(CN)2 or CuCN
  • a suitable solvent e.g. dimethylformamide or N-methylpyrrolidone
  • Compounds of formula (VI), wherein V is Br or I, or CN can be prepared from compounds of formula (VIII), wherein X is F, CI, Br, I, or OSCteMe, via treatment with compounds of formula (II), in the presence of a base (e.g. lithium hexamethyldisilylazide, n- butyllithium, CS2CO3, CSF, K2CO3 or NaH) in a suitable solvent (e.g. dimethylformamide, acetone or tetrahydrofuran) at a temperature between -78°C and 25°C.
  • a base e.g. lithium hexamethyldisilylazide, n- butyllithium, CS2CO3, CSF, K2CO3 or NaH
  • a suitable solvent e.g. dimethylformamide, acetone or tetrahydrofuran
  • Compounds of formula (VII) (i.e., compounds of Formula (VI) wherein R 5 is H) wherein V is Br, I, or CN, can be prepared from carbonyl compounds of formula (IX), via treatment with compounds of formula (II) in the presence of a base, such as triethylamine, in a suitable solvent (eg, methanol or ethanol) at a temperature between 0°C and 100°C; followed by the addition of a reducing reagent (e.g. NaBhU or NaBh CN).
  • a base such as triethylamine
  • a suitable solvent eg, methanol or ethanol
  • a reducing reagent e.g. NaBhU or NaBh CN
  • compounds of formula (VIII), wherein X is CI, Br, I, or OSCteMe are either commercially available or can be prepared from compounds of formula (X), wherein V is Br, I or CN, by treatment with a halogen source (eg, CBr4, CCU or ) in the presence of triphenylphosphine, or with methanesulfonyl chloride (CISChMe), in a suitable solvent, (eg, dichloromethane or 1 ,2- dichloroethane) at a temperature between 0°C and 80°C.
  • a halogen source eg, CBr4, CCU or
  • CISChMe methanesulfonyl chloride
  • suitable solvent eg, dichloromethane or 1 ,2- dichloroethane
  • (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® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl ) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bl ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as ⁇ -endotoxins, e.g. CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp.
  • insecticidal proteins from Bacillus cereus or Bacillus popilliae such as ⁇ -endotoxins, e.g. CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl- transferase, cholesterol oxidases, ecdy
  • ⁇ -endotoxins for example CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins.
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ).
  • Truncated toxins for example a truncated CrylAb, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • amino acid replacements preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO93/07278, W095/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
  • Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
  • Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses a
  • transgenic crops are:
  • Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylAb toxin. Bt1 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
  • MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810. 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 as used herein means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
  • plants refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
  • plant propagation material is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes.
  • vegetative material such as cuttings or tubers, for example potatoes.
  • seeds in the strict sense
  • roots in the strict sense
  • fruits in the tubers
  • bulbs rhizomes
  • parts of plants there can be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants.
  • Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil may also be mentioned. These young plants can be protected before transplantation by a total or partial treatment by immersion.
  • plant propagation material is understood to denote seeds.
  • the compounds of formula I may be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation.
  • compositions 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.
  • the methods of application such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • the compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
  • Suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers.
  • Such carriers are for example described in WO 97/33890.
  • Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations include anti-settling agents and dispersing agents and may further include a wetting agent to enhance activity as well an anti-foam and a crystal growth inhibitor. In use, these concentrates are diluted in water and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
  • Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers.
  • the particles contain the active ingredient retained in a solid matrix.
  • Typical solid matrices include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.
  • Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other nonvolatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
  • Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required.
  • Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound.
  • Granular formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; 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.
  • 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.
  • 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
  • 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.
  • alcohol-alkylene oxide addition products such as tridecyl alcohol-C.sub. 16 ethoxylate
  • soaps such as sodium stearate
  • alkylnaphthalenesulfonate salts such as sodium dibutylnaphthalenesulfonate
  • dialkyl esters of sulfosuccinate salts such as sodium di(2-ethylhexyl) sulfosuccinate
  • sorbitol esters such as sorbitol oleate
  • quaternary amines such as lauryl trimethylammonium chloride
  • polyethylene glycol esters of fatty acids such as polyethylene glycol stearate
  • salts of mono and dialkyl phosphate esters such as mono and dialkyl phosphate esters.
  • adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, anti-foaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and sticking agents.
  • biocidally active ingredients or compositions may be combined with the compositions of the invention and used in the methods of the invention and applied simultaneously or sequentially with the compositions of the invention. When applied simultaneously, these further active ingredients may be formulated together with the compositions of the invention or mixed in, for example, the spray tank. These further biocidally active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.
  • Pesticidal agents are referred to herein using their common name are known, for example, from “The Pesticide Manual”, 15th Ed., British Crop Protection Council 2009.
  • compositions of the invention may also be applied with one or more system ically acquired resistance inducers ("SAR" inducer).
  • SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.
  • the compounds of formula (I) are normally used in the form of agrochemical compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds.
  • further compounds can be e.g. fertilizers or micronutrient donors or other preparations, which influence the growth of plants. They can also be selective herbicides or non- selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
  • the compounds of formula (I) may be used in the form of (fungicidal) compositions for controlling or protecting against phytopathogenic microorganisms, comprising as active ingredient at least one compound of formula (I) or of at least one preferred individual compound as defined herein, in free form or in agrochemically usable salt form, and at least one of the above-mentioned adjuvants.
  • the invention therefore provides a composition, preferably a fungicidal composition, comprising at least one compound formula (I) an agriculturally acceptable carrier and optionally an adjuvant.
  • An agricultural acceptable carrier is for example a carrier that is suitable for agricultural use.
  • Agricultural carriers are well known in the art.
  • said composition may comprise at least one or more 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- 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
  • the compounds of the invention may also be used in combination with anthelmintic agents.
  • anthelmintic agents include, compounds selected from the macrocyclic lactone class of compounds such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin derivatives as described in EP- 357460, EP- 444964 and EP-594291.
  • Additional anthelmintic agents include semisynthetic and biosynthetic avermectin/milbemycin derivatives such as those described in US-5015630, WO-9415944 and WO- 9522552. Additional anthelmintic agents include the benzimidazoles such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, and other members of the class. Additional anthelmintic agents include imidazothiazoles and tetrahydropyrimidines such as tetramisole, levamisole, pyrantel pamoate, oxantel or morantel. Additional anthelmintic agents include flukicides, such as triclabendazole and clorsulon and the cestocides, such as praziquantel and epsiprantel.
  • the compounds of the invention may be used in combination with derivatives and analogues of the paraherquamide/marcfortine class of anthelmintic agents, as well as the antiparasitic oxazolines such as those disclosed in US-5478855, US- 4639771 and DE-19520936.
  • the compounds of the invention may be used in combination with derivatives and analogues of the general class of dioxomorpholine antiparasitic agents as described in WO 96/15121 and also with anthelmintic active cyclic depsipeptides such as those described in WO 96/11945, WO 93/19053, WO 93/25543, EP 0 626 375, EP 0 382 173, WO 94/19334, EP 0 382 173, and EP 0 503 538.
  • the compounds of the invention may be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.
  • ectoparasiticides for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.
  • the compounds of the invention may be used in combination with terpene alkaloids, for example those described in International Patent Application Publication Numbers WO 95/19363 or WO 04/72086, particularly the compounds disclosed therein.
  • Organophosphates acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, bromophos, bromophos-ethyl, cadusafos, chlorethoxyphos, chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demeton-S-methyl, demeton-S-methyl sulphone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosthiazate, heptenophos, isazophos, isothioate, isoxathion, malathion, me
  • Carbamates alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801 , isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenylbutyryl(methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, UC-51717.
  • Pyrethroids acrinathin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E) -(1 R)-cis-2,2- dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, bifenthrin, beta -cyfluthrin, cyfluthrin, a-cypermethrin, beta -cypermethrin, bioallethrin, bioallethrin((S)-cyclopentylisomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin, cythithrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, ethofenprox, fenfluthrin, fenpropathrin, 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 compound0 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 of5 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 the0 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
  • 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 by5 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 drenching0 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 ingre- dominant species 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 1a discloses 46 combinations (compounds 1a.001 to 1a.046) of A 1 , A 2 , A 3 , A 4 ,
  • Formula (T-1 ) corresponds to Formula (I) as defined for the present invention.
  • Tables 2a to 22a make available 46 additional individual compounds of the formula (T-1 ) in which Z and R 6 are as specifically defined in Tables 2a to 22a (Formulae T-1a.2 to T-1a.22), which refer to Table 1a wherein A 1 , A 2 , A 3 , A 4 , R 5 , R 7 and R 8 are specifically defined.
  • Table 1a :
  • Table 3a This table discloses compounds 3a.001 to 3a.046 of the formula (T-1a.3), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 and R 8 have the specific meanings iven in the Table 1a.
  • Table 4a This table discloses compounds 4a.001 to 4a.046 of the formula (T-1a.4), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 and R 8 have the specific meanings given in the Table 1a.
  • Table 5a This table discloses compounds 5a.001 to 5a.046 of the formula (T-1a.5), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 and R 8 have the specific meanings given in the Table 1a.
  • Table 6a This table discloses compounds 6a.001 to 6a.046 of the formula (T-1a.6), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 and R 8 have the specific meanings given in the Table 1a.
  • Table 7a This table discloses compounds 7a.001 to 7a.046 of the formula (T-1a.7), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 and R 8 have the specific meanings given in the Table 1a.
  • Table 8a This table discloses compounds 8a.001 to 8a.046 of the formula (T-1a.8), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 and R 8 have the specific meanings given in the Table 1a.
  • Table 9a This table discloses compounds 9a.001 to 9a.046 of the formula (T-1a.9), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 and R 8 have the specific meanings given in the Table 1a.
  • Table 10a This table discloses compounds 10a.001 to 10a.046 of the formula (T-1a.10), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 and R 8 have the specific meanings given in the Table 1a.
  • Table 1 1a This table discloses compounds 1 1a.001 to 1 1a.046 of the formula (T-1a.1 1 ), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 and R 8 have the specific meanin s given in the Table 1a.
  • Table 12a This table discloses compounds 12a.001 to 12a.046 of the formula (T-1a.12), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 and R 8 have the specific meanings given in the Table 1a.
  • Table 13a This table discloses compounds 13a.001 to 13a.046 of the formula (T-1a.13), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 and R 8 have the specific meanin s given in the Table 1a.
  • Table 14a This table discloses compounds 14a.001 to 14a.046 of the formula (T-1a.14), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 and R 8 have the specific meanings given in the Table 1.
  • Table 15a This table discloses compounds 15a.001 to 15a.046 of the formula (T-1a.15), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 and R 8 have the specific meanin s given in the Table 1a.
  • Table 16a This table discloses compounds 16a.001 to 16a.046 of the formula (T-1a.16), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 and R 8 have the specific meanin s given in the Table 1a.
  • Table 17a This table discloses compounds 17a.001 to 17a.046 of the formula (T-1a.17), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 and R 8 have the specific meanings given in the Table 1a.
  • Table 18a This table discloses compounds 18a.001 to 18a.046 of the formula (T-1a.18), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 and R 8 have the specific meanings given in the Table 1 a.
  • Table 19a This table discloses compounds 19a.001 to 19a.046 of the formula (T-1a.19), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 and R 8 have the specific meanin s given in the Table 1a.
  • Table 20a This table discloses compounds 20a.001 to 20a.046 of the formula (T-1a.20), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 and R 8 have the specific meanin s given in the Table 1a.
  • Table 21 a This table discloses compounds 21a.001 to 21 a.046 of the formula (T-1a.21 ), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 and R 8 have the specific meanin s given in the Table 1a.
  • Table 22a This table discloses compounds 22a.001 to 22a.046 of the formula (T-1a.22), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 and R 8 have the specific meanings given in the Table 1a.
  • Table 1b discloses 138 combinations (compounds 1b.001 to 1b.138) of A 1 , A 2 , A 3 , A 4 , R 5 , R 7 , R 8 and R 9 substituents in accordance with compounds as defined for Formula (T-1), wherein heterocycle Z contains a NR 9 ring member.
  • Formula (T-1) corresponds to Formula (I) as defined for the present invention.
  • Tables 2b to 4b make available 138 additional individual compounds of the formula (T-1) in which Z and R 6 are as specifically defined in Tables 2b to 4b (Formulae T-1b.2 to T-1b.4), which refer to Table 1b wherein A 1 , A 2 , A 3 , A 4 , R 5 , R 7 , R 8 and R 9 are specifically defined.
  • Table 2b This table discloses compounds 2b.001 to 2b.138 of the formula (T-1b.2), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 , R 8 and R 9 have the specific meanings given in the Table 1b.
  • Table 3b This table discloses compounds 3b.001 to 3b.138 of the formula (T-1b.3), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 , R 8 and R 9 have the specific meanin s given in the Table 1b.
  • Table 4b This table discloses compounds 4b.001 to 4b.138 of the formula (T-1b.4), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 , R 8 and R 9 have the specific meanin s given in the Table 1b.
  • Table 1c discloses 690 combinations (compounds 1c.001 to 1c.690) of A 1 , A 2 , A 3 , A 4 , R 5 , R 7 , R 8 , R 9 , R 0 and R substituents in accordance with compounds as defined for Formula (T-1), wherein heterocycle Z contains a NR 9 ring member.
  • Formula (T-1) corresponds to Formula (I) as defined for the present invention.
  • Table 2c (which follows Table 1c) makes available 690 additional individual compounds of the formula (T-1) in which Z and R 6 are as specifically defined in Table 2c (Formula T-1c.2), which refers to Table 1c wherein A 1 , A 2 , A 3 , A 4 , R 5 , R 7 , R 8 , R 9 , R 0 and R are specifically defined.
  • Table 2c This table discloses compounds 2c.001 to 2c.690 of the formula (T-1c.2), which is a compound of formula (I) wherein R 6 is H and A 1 , A 2 , A 3 , A 4 , R 5 , R 7 , R 8 , R 9 , R 0 and R have the s ecific meanings given in the Table 1c.
  • Table 1d discloses 30 combinations (compounds 1d.001 to 1d.030) of A 1 , A 2 , A 3 , A 4 , R 7 and R 8 substituents in accordance with compounds as defined for Formula (T-2).
  • Formula (T-2) corresponds to Formula (I) as defined for the present invention.
  • Tables 2d to 13d make available 30 additional individual compounds of the formula (T-2) in which Z is as specifically defined in Tables 2d to 13d (Formulae T- 2d.2 to T-2d.13), which refer to Table 1d wherein A 1 , A 2 , A 3 , A 4 , R 7 and R 8 are specifically defined.
  • Table 2d This table discloses compounds 2d.001 to 2d.030 of the formula (T-2d.2), which is a compound of formula (I) wherein A 1 , A 2 , A 3 , A 4 , R 7 and R 8 have the specific meanings given in the Table 1d.
  • Table 3d This table discloses compounds 3d.001 to 3d.030 of the formula (T-2d.3), which is a compound of formula (I) wherein A 1 , A 2 , A 3 , A 4 , R 7 and R 8 have the specific meanings given in the Table 1d.
  • Table 4d This table discloses compounds 4d.001 to 4d.030 of the formula (T-2d.4), which is a compound of formula (I) wherein A 1 , A 2 , A 3 , A 4 , R 7 and R 8 have the specific meanings given in the Table 1 d.
  • Table 5d This table discloses compounds 5d.001 to 5d.030 of the formula (T-2d.5), which is a compound of formula (I) wherein A 1 , A 2 , A 3 , A 4 , R 5 , R 7 and R 8 have the specific meanings given in the Table 1 d.
  • Table 6d This table discloses compounds 6d.001 to 6d.030 of the formula (T-2d.6), which is a compound of formula (I) wherein A 1 , A 2 , A 3 , A 4 , R 7 and R 8 have the specific meanings given in the Table 1 d.
  • Table 7d This table discloses compounds 7d.001 to 7d.030 of the formula (T-2d.7), which is a compound of formula (I) wherein A 1 , A 2 , A 3 , A 4 , R 7 and R 8 have the specific meanings given in the Table 1 d.
  • Table 8d This table discloses compounds 8d.001 to 8d.030 of the formula (T-2d.8), which is a compound of formula (I) wherein A 1 , A 2 , A 3 , A 4 , R 7 and R 8 have the specific meanings given in the Table 1 d.
  • Table 9d This table discloses compounds 9d.001 to 9d.030 of the formula (T-2d.9), which is a compound of formula (I) wherein A 1 , A 2 , A 3 , A 4 , R 7 and R 8 have the specific meanings given in the Table 1 d.
  • Table 10d This table discloses compounds 10d.001 to 10d.030 of the formula (T-2d.10), which is a compound of formula (I) wherein A 1 , A 2 , A 3 , A 4 , R 7 and R 8 have the specific meanings given in the Table 1 d.
  • Table 1 1 d This table discloses compounds 1 1d.001 to 1 1 d.030 of the formula (T-2d.1 1 ), which is a compound of formula (I) wherein A 1 , A 2 , A 3 , A 4 , R 7 and R 8 have the specific meanings given in the Table 1 d.
  • Table 12d This table discloses compounds 12d.001 to 12d.030 of the formula (T-2d.12), which is a compound of formula (I) wherein A 1 , A 2 , A 3 , A 4 , R 7 and R 8 have the specific meanings given in the Table 1 d.
  • Table 13d This table discloses compounds 13d.001 to 13d.030 of the formula (T-2d.13), which is a compound of formula (I) wherein A 1 , A 2 , A 3 , A 4 , R 7 and R 8 have the specific meanings given in the Table 1 d.
  • the compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.
  • Compounds of Formula (I) may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against diseases that are caused by fungi or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).
  • LC/MS Liquid Chromatography Mass Spectrometry and the description of the apparatus and the method is as follows:
  • 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.
  • Electrospray Polarity positive ions
  • Type of column Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1 .8 micron; Temperature: 60°C.
  • Type of column Waters ACQUITY UPLC BEH C18; Column length: 50 mm; Internal diameter of column: 2.1 mm; Particle Size: 1 .7 micron; Temperature: 35°C.
  • enantiomerically pure final compounds may be obtained from racemic materials as appropriate via standard physical separation techniques, such as reverse phase chiral chromatography, or through stereoselective synthetic techniques, eg, by using chiral starting materials.
  • the active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
  • the active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
  • Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water. Dusts a) b) c)
  • Active ingredient [compound of formula (I)] 5 % 6 % 4 %
  • Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
  • the active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • polyethylene glycol (mol. wt. 200) 3 %
  • Kaolin 89 % The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
  • nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
  • silicone oil (in the form of a 75 % emulsion in water) 1 %
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • Flowable concentrate for seed treatment active ingredient [compound of formula (I)] 40 %
  • Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • 28 parts of a combination of the compound of formula I are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8: 1 ).
  • This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved.
  • To this emulsion a mixture of 2.8 parts 1 ,6- diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
  • AIBN azobisisobutyronitrile
  • DIPEA N,N-di-isopropylethylamine
  • KHMDS potassium bis(trimethylsilyl)amide
  • NaOH sodium hydroxide
  • NBS N-bromosuccinimide
  • Example 1 This example illustrates the preparation 2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]isoxazolidin-3-one (Compound A-5 of Table A)
  • Step 3a Preparation of 3-[4-(bromomethyl)phenyll-5-(trifluoromethvn-1 ,2,4-oxadiazole
  • Step 3b Preparation of 3-[4-(bromomethyl)phenyll-5-(trifluoromethyl)-1 ,2,4-oxadiazole from 3-[4-
  • Step 4 Preparation of 2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyllisoxazolidin-3-one
  • Example 2 This example illustrates the preparation of 4,4-dimethyl-1-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]piperidine-2,6-dione (Compound A-1 1 of Table A)
  • Example 3 This example illustrates the preparation of 4-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]morpholin-3-one Compound A-3 of Table A)
  • Example 4 This example illustrates the preparation of 1-[[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2- pyridyl]methyl]piperidin-2-one (Compound A-12 of Table A)
  • Step 1 N'-hvdroxy-6-methyl-pyridine-3-carboxamidine
  • Step 2 Preparation of 3-(6-methyl-3-pyridyl)-5-(trifluoromethyl)-1 ,2,4-oxadiazole
  • Step 3a Preparation of 3-[6-(bromomethyl)-3-pyridyll-5-(trifluoromethyl)-1 ,2,4-oxadiazole
  • Step 3b Preparation of 3-[6-(bromomethyl)-3-pyridyll-5-(trifluoromethyl)-1 ,2,4-oxadiazole
  • Step 4 Preparation of 1-[[5-[5-(trifluoromethvn-1 ,2,4-oxadiazol-3-yll-2-pyridyllmethyllpiperidin-2-one
  • reaction mixture was quenched at 0°C with a sat. NH4CI solution and the solution extracted with ethyl acetate.
  • the combined organic layers were washed with brine, dried over sodium sulfate, filtered, concentrated and purified by combiflash chromatography over silica gel using a cyclohexane/AcOEt as eluent to afford 0.21 g of the title compound as yellow oil.
  • Example 5 This example illustrates the preparation of 2-[[2-chloro-4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]-1 ,2-thiazolidine 1 , 1-dioxide (Compound B-2 of Table B )
  • Example 6 This example illustrates the preparation of 2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]-1 ,2-thiazolidine 1 , 1 -dioxide (Compound D-1 of Table D)
  • Step 2 4-(1 ,1-dioxo-1 ,2-thiazolidi
  • Example 7 This example illustrates the preparation of 2 2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]isoxazolidin-3-one (Compound C-2 of Table C)
  • Step 1 4-(3-oxoisoxazolidin-2-yl)benzonitrile
  • a sealed tube was charged with 4-iodobenzonitrile (1.0 g, 4.4 mmol), isoxazolidin-3-one (1 .2 equiv.; 0.46 g, 5.2 mmol), dimethylethylenediamine (0.1 equiv., 0.47 mL, 0.44 mmol), cesium fluoride (2.5 equiv., 1.66 g, 10.9 mmol), copper iodide (0.05 equiv., 0.04 g, 0.20 mmol), tetrahydrofuran (8 imL) and the reaction contents were stirred at room temperature for 24 hours. The reaction contents were diluted with ethyl acetate and a saturated aqueous ammonium chloride solution.
  • Step 3 2 2-[4-[5-(trifluoromethvn-1 ,2,4-oxadiazol-3-yllphenyllisoxazolidin-3-one
  • Example 8 This example illustrates the preparation of tert-butyl 3-oxo-4-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]meth l]piperazine-1-carboxylate (Compound A-30 of Table A)
  • reaction mixture was quenched at 0°C with a 1 M HCI solution and the mixture was extracted with EtOAc. The combined organic layers were washed with brine, dried over Na2S04, filtered, concentrated and purified by Isco combiflash Rf using cyclohexane/AcOEt as eluent to give tert-butyl 3-oxo-4-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]piperazine-1-carboxylate as a white solid.
  • Example 9 This example illustrates the preparation of N,N-dimethyl-3-oxo-4-[[4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]phenyl]meth l]piperazine-1-carboxamide (Compound A-34 of Table A)
  • Step 1 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyllpiperazin-2-one hydrochloride (Compound A-36 of Table A)
  • Step 2 N,N-dimethyl-3-oxo-4-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyllpiperazine-1- carboxamide
  • Example 10 This example illustrates the preparation of N,N-dimethyl-3-oxo-4-[[4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]phenyl]methyl]piperazine-1-sulfonamide (Compound A-42 of Table A)
  • Example 1 1 This example illustrates the preparation of 1-methoxy-3-[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]imidazolidin-2-one Compound C-3 of Table C)
  • Step 1 1-methoxy-3-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllurea
  • the solid obtained was further purified by recrystallization from CH2CI2 and MeOH to give 1-methoxy-3-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]imidazolidin-2-one as white crystals.
  • Example 12 This example illustrates the preparation 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]azepan-2-one (Compound A-70 of Table A)
  • reaction mixture was quenched at 0°C with a saturated ammonium chloride solution and extracted with ethyl acetate.
  • the total combined organic layer was washed with brine, dried over Na2S04, filtered, and concentrated under reduced pressure.
  • the crude residue was purified by combiflash column chroatography (cyclohexane/ethyl acetate eluent gradient 1 :0 to 1 : 1 ) to give 1-[[4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]phenyl]methyl]azepan-2-one as a colourless oil. (75 mg, 27% yield).
  • enantiomerically pure final compounds may be obtained from racemic materials as appropriate via standard physical separation techniques, such as reverse phase chiral chromatography, or through stereoselective synthetic techniques, (eg, by using chiral starting materials).
  • Leaf disks or leaf segments of various plant species are cut from plants grown in a greenhouse.
  • the cut leaf disks or segments are placed in multiwell plates (24-well format) onto water agar.
  • the leaf disks are sprayed with a test solution before (preventative) or after (curative) inoculation.
  • Compounds to be tested are prepared as DMSO solutions (max. 10 mg/ml) which are diluted to the appropriate 10 concentration with 0.025% Tween20 just before spraying.
  • the inoculated leaf disks or segments are incubated under defined conditions (temperature, relative humidity, light, etc.) according to the respective test system.
  • a single evaluation of disease level is carried out 3 to 14 days after inoculation, depending on the pathosystem. Percent disease control relative to the untreated check leaf disks or segments is then calculated.
  • Mycelia fragments or conidia suspensions of a fungus prepared either freshly from liquid cultures of the fungus or from cryogenic storage, are directly mixed into nutrient broth.
  • test compound (max. 10 mg/ml) is diluted with 0.025% Tween20 by a factor of 50 and 10 ⁇ of this solution is pipetted into a microtiter plate (96-well format). The nutrient broth containing the fungal spores/mycelia fragments is then added to give an end concentration of the tested compound. The test plates are incubated in the dark at 24 °C and 96% relative humidity. The inhibition of fungal growth is determined photometrically after 2 to 7 days, depending on the pathosystem, and percent
  • Example 1 Fungicidal activity against Glomerella lagenarium (Colletotrichum lagenarium) liquid culture / cucumber / preventative (Anthracnose)
  • Example 2 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 - 14 days after application).
  • Example 3 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 inoculated with a spore suspension of the fungus. Plates are stored in darkness at 19 °C and 75% rh. The formulated test compound diluted in water is applied 1 day after inoculation. The leaf segments are incubated at 19 °C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and 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 segments (6 - 8 days after application).
  • Wheat leaf segments cv. Kanzler are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf segments are inoculated with a 15 spore suspension of the fungus 1 day after application.
  • the inoculated leaf segments are incubated at 19 °C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and 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 segments (7 - 9 days after application).
  • Example 5 Fungicidal activity against Uromyces viciae-fabae I field bean / leaf disc preventative (Faba-bean rust)
  • Field bean leaf discs are placed on water agar in multiwell plates (96-well format) and 10 ⁇ of the formulated test compound diluted in acetone and a spreader pipetted onto the leaf disc. Two hours after application leaf discs are inoculated by spraying a spore suspension on the lower leaf surface. The leaf discs are incubated in a climate cabinet at 22°C with 18 hour day and 70% relative humidity. 40 The activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (12 days after application).

Abstract

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

Description

Microbiocidal Oxadiazole Derivatives
The present invention relates to microbiocidal oxadiazole derivatives, eg, as active ingredients, which have microbiocidal activity, in particular, fungicidal activity. The invention also relates to agrochemical compositions which comprise at least one of the oxadiazole derivatives, to processes of preparation of these compounds and to uses of the oxadiazole derivatives or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, preferably fungi.
According to the present invention, there is rovided a compound of formula (I):
Figure imgf000002_0001
n is 0 or 1 or 2;
A1 represents N or CR\ wherein R represents hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy;
A2 represents N or CR2, wherein R2 represents hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy;
A3 represents N or CR3, wherein R3 represents hydrogen or halogen;
A4 represents N or CR4, wherein R4 represents hydrogen or halogen; and wherein no more than two of A1 to A4 are N;
R5 and R6 independently represent hydrogen, halogen, cyano, difluoromethyl, trifluoromethyl, or Ci-4alkyl, or together with the carbon atom to which they are bonded represent cyclopropyl;
Z represents a roup selected from Z-1 , Z-2, Z-3 or Z-4:
Figure imgf000002_0002
(Z-1 ) (Z-2) (Z-3) (Z-4) wherein: represents C(O) or S(0)2; and
B and B2 in Z-1 represent C(R7)(R8); or
(ϋ) B\ B2 and B3 in Z-2 independently represent C(R7)(R8), O, S, NR9 or C(=0), wherein only one of B\ B2 and B3 may be a group selected from O, S, NR9 or C(=0); or (iii) B\ B2, B3 and B4 in Z-3 independently represent C(R7)(R8), O, S, NR9 or C(=0), wherein only one of B\ B2, B3 and B4 may be a group selected from O, S or C(=0), and only one of B\ B2, B3 and B4 may be NR9; or (iv) B in Z-2 is C(R7)(R8) and B2-B3 is a group selected from NR9C(=0), C(=0)NR9, N=N, C(R7)=C(R8), C(R8)=N or N=C(R8); or B3 in Z-2 is C(R7)(R8) and B -B2 is a group selected from NR9C(=0), C(=0)NR9, N=N, C(R7)=C(R8), C(R8)=N or N=C(R8); or
(v) B and B2 in Z-3 are C(R7)(R8) and B3-B4 is a group selected from NR9C(=0), C(=0)NR9, N=N, C(R7)=C(R8), C(R8)=N or N=C(R8); B and B4 in Z-3 are C(R7)(R8) and B2-B3 is a group selected from NR9C(=0), C(=0)NR9, N=N, C(R7)=C(R8), C(R8)=N or N=C(R8); or B3 and B4 in Z-3 are C(R7)(R8) and B -B2 is a group selected from NR9C(=0), C(=0)NR9, N=N, C(R7)=C(R8), C(R8)=N or N=C(R8); or (vi) B1, B2, B3, B4 and B5 in Z-4 independently represent C(R7)(R8), O, S, NR9 or C(=0), wherein only one of B\ B2, B3, B4 and B5 may be a group selected from O, S, NR9 or C(=0); or represents a group selected from Z-5, wherein Z-5 represents Z-5a, Z-5b, Z-5c, Z-5d, Z-5e, Z-5f or Z-5 :
Figure imgf000003_0001
(Z-5a) (Z-5b) (Z-5c)
Figure imgf000004_0001
(Z-5d) (Z-5e) (Z-5f) (Z-5g) wherein a is 0, 1 , 2 or 3; or
Z represents a group selected from Z-6, wherein Z-6 represents Z-6a, Z-6b, Z-6c or Z-6d:
Figure imgf000004_0002
wherein Y is Ci-4alkylene or C(R7)=C(R8);
R7 and R8 independently represent hydrogen, halogen, Ci C4alkyl, Ci C4haloalkyl or Ci- C4alkoxy; R9 represents hydrogen, d ealkyl, Cs ealkenyl, Cs ealkynyl, C3-6cycloalkyl, d ealkoxy, C(0)R10,
C(0)OR10, C(O)N(R 0)R11, S(0)2R10 or S(O)2N(R 0)R \ wherein Ci-6alkyl, C3-6alkenyl, C3-6alkynyl, C3- 6cycloalkyl and d ealkoxy are optionally substituted by halogen or cyano;
R 0 represents hydrogen, d ealkyl, d ecycloalkyl, d-6cycloalkyld-2alkyl, d-4alkoxyd-4alkyl, wherein d ealkyl, d ecycloalkyl, d-6cycloalkyld-2alkyl and d-4alkoxyd-4alkyl are optionally substituted by halogen or cyano; and
R represents hydrogen, d-4alkyl, d-4haloalkyl, d-4alkoxy or d-4alkoxy-d-4alkyl; 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).
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 exclude 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, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
As used herein, cyano means a -CN group.
As used herein, the term "Ci-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 "Ci-4alkyl" and "Ci-2alkyl" are to be construed accordingly. Examples of d ealkyl include, but are not limited to, methyl, ethyl, n-propyl, 1-methylethyl (iso-propyl), n-butyl,1-dimethylethyl (i-butyl) and n-pentyl. A "Ci- 4alkylene" group refers to a corresponding definition of Ci-C4alkyl, except that such radical is attached to the rest of the molecule by two single bonds. The term "C2-4alkylene" is to be construed accordingly. Examples of Ci C4alkylene, include, but are not limited to, -CH2-, -CH2CH2- and -(CH2)3-.
As used herein, the term "Cs ealkenyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one double bond that can be of either the (E)- or (Z)-configu ration, having from three to six carbon atoms, which is attached to the rest of the molecule by a single bond . Examples of Cs ealkenyl include, but are not limited to, prop- 1-enyl, but-1-enyl.
As used herein, the term "Cs ealkynyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having from three to six carbon atoms, and which is attached to the rest of the molecule by a single bond. Examples of Cs ealkynyl include, but are not limited to, prop-1-ynyl, but-1-ynyl.
As used herein, the term "Ci ealkoxy" refers to a radical of the formula -ORa where Ra is a C1-6 alkyl radical as generally defined above. The term "C1-C4 alkoxy" is to be construed accordingly. Examples of d ealkoxy include, but are not limited to, methoxy, ethoxy, propoxy, iso-propoxy, butoxy.
As used herein, the term "Ci-4haloalkyl" refers to a Ci-4alkyl radical as generally defined above substituted by one or more of the same or different halogen atoms. Examples of Ci-4haloalkyl include, but are not limited to fluoromethyl, difluoromethyl, fluoroethyl, trifluoromethyl, 2,2,2-trifluoroethyl.
As used herein, the term "C3-6cycloalkyl" refers to a monocyclic radical and contains 3 to 6 carbon atoms. Examples of C3-6cycloalkyl include, but are not limited to, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. As used herein, the term "C3-6cycloalkylCi-2alkyl" refers to a C3-6cycloalkyl ring as defined above attached to the rest of the molecule by a Ci-2alkylene radical as defined above. Examples of C3- 6cycloalkylCi-2alkyl include, but are not limited to cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclopentylmethyl and cyclohexylmethyl.
As used herein, the term "Ci-4alkoxyCi-4alkyl" refers to a Ci-4alkyl radical as generally defined above substituted by a Ci-4alkoxy group as defined above. Examples of Ci-4alkoxyCi-4alkyl include, but are not limited to methoxymethyl, 2-methoxyethyl.
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, X, A1 , A2, A3, A4, R\ R2, R3, R4, R5, R6, Z (including Z-1 , Z-2, Z-3, Z-4, Z-5 (Z-5a to Z-5g) and Z-6 (Z-6a to Z- 6d)), R7, R8, R9, R 0, R , a and Y 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 is 0 or 1 or 2. In one embodiment of the invention, n is 1. In another embodiment of the invention, n is 0. In a further embodiment of the invention, n is 2. X represents C(O) or S(0)2. In one embodiment of the invention, X is C(O). In another embodiment of the invention, X is S(0)2.
A1 represents N or CR\ wherein R represents hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy. In one embodiment of the invention, A1 is CR . Preferably, R represents hydrogen, halogen, methyl, trifluoromethyl or methoxy. More preferably, R represents hydrogen, halogen or methyl. Even more preferably, R represents hydrogen or fluoro. Most preferably, R represents hydrogen. In another embodiment of the invention, A1 is N.
A2 represents N or CR2, wherein R2 represents hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy. In one embodiment of the invention, A2 is CR2. Preferably, R2 represents hydrogen, halogen, methyl, trifluoromethyl or methoxy. More preferably, R2 represents hydrogen or methyl. In another embodiment of the invention, A2 is N.
A3 represents N or CR3, wherein R3 represents hydrogen or halogen. In one embodiment of the invention, A3 represents CR3. Preferably, R3 represents hydrogen.
A4 represents N or CR4, wherein R4 represents hydrogen or halogen. In one embodiment of the invention, A4 represents CR4. Preferably, R4 represents hydrogen. In the compounds of Formula (I) according to the invention, no more than two of A1 to A4 are
N, in particular, at least two of R to R4 may be hydrogen. Preferably, at least R2, R3 and R4 are hydrogen. In other embodiments, (i) A1 is CR1 and R is hydrogen, and A2 is CR2 and R2 is hydrogen; (ii) A1 is CR1 and R is halogen, and A2 is CR2 and R2 is hydrogen; or (iii) A1 is N and A2 is CR2 and R2 is hydrogen. Preferably, A3 is CR3 and R3 is hydrogen, and A4 is CR4 and R4 is hydrogen.
In some embodiments of the invention, the 6-membered ring comprising A1 to A4 is a phenyl (where A1 , A2, A3 and A4 are C-H), a pyridinyl (where A1 is N and A2, A3 and A4 are C-H, or A3 is N and A1 , A2 and A4 are C-H), a fluorophenyl (where A1 is C-F and A2, A3 and A4 are C-H, or A3 is C-F and A1 , A2 and A4 are C-H) or a difluorophenyl (eg, where A1 and A2 are C-F and A3 and A4 are C-H, or A1 and A3 are C-F and A2 and A4 are C-H) group.
R5 and R6 independently represent hydrogen, halogen, cyano, difluoromethyl, trifluoromethyl, or Ci-4alkyl, or together with the carbon atom to which they are bonded represent cyclopropyl. Preferably, R5 and R6 are hydrogen, or R5 is hydrogen and R6 is methyl, or R5 and R6 are methyl. Most preferably, R5 and R6 are hydrogen.
Z represents a group selected from Z-1 , Z-2, Z-3, Z-4, Z-5 (Z-5a, Z-5b, Z-5c, Z-5d, Z-5e, Z-5f, Z- 5g) or Z-6 (Z-6a, Z-6b, Z-6c, Z-6d) as defined herein. Preferably, Z represents Z-1 , Z-2 or Z-3, and, in particular Z-2 or Z-3. More preferably, Z represents Z-1 , Z-2 or Z-3 when X is C(O), and, in particular Z represents Z-2 or Z-3, when X is C(O).
In some embodiments of the invention, Z represents:
Z-1 wherein B and B2 represent C(R7)(R8);
Z-2 wherein B\ B2 and B3 independently represent C(R7)(R8), O, NR9 or C(=0), wherein only one of B\ B2 and B3 may be O, NR9 or C(=0); Z-3 wherein B\ B2, B3 and B4 independently represent C(R7)(R8), NR9 or C(=0), wherein one of B1, B2, B3 and B4 may be NR9 and one of B\ B2, B3 and B4 may be C(=0);
Z-3 wherein B\ B2, B3 and B4 independently represent C(R7)(R8), O, NR9 or C(=0), wherein only one of B\ B2, B3 and B4 may be O, NR9 or C(=0);
Z-6a wherein Y represents C(R7)=C(R8); or Z-6c wherein Y represents C2-4alkylene.
More preferably, Z represents:
Z-2 wherein B and B3 independently represent C(R7)(R8), O, NR9 or C(=0) wherein only one of B and B3 may be a O, NR9 or C(=0), and B2 represents C(R7)(R8); or
Z-3 wherein B\ B2 and B4 independently represent C(R7)(R8), O, NR9 or C(=0) wherein only one of B\ B2 and B4 may be O, NR9 or C(=0), and B3 represents C(R7)(R8).
In other embodiments of the invention, Z represents:
Z-2 wherein B and B3 independently represent C(R7)(R8), O or C(=0) wherein only one of B and B3 may be O or C(=0), and B2 represents C(R7)(R8), wherein R7 and R8, independently of each other, are selected from hydrogen or Ci- 4alkyl; or
Z-2 wherein B and B2 are C(R7)(R8) wherein R7 and R8, independently of each other, are selected from hydrogen or Ci-4alkyl (and preferably hydrogen or methyl), and B3 is O or C(=0) (and preferably O); or
Z-3 wherein B\ B2 and B4 independently represent C(R7)(R8), O, NR9 or C(=0) wherein only one of B\ B2 and B4 may be a O, NR9 or C(=0), and B3 represents C(R7)(R8), wherein R7 and R8, independently of each other, are selected from hydrogen or Ci- 4alkyl; or
Z-3 wherein B , B2 and B3 are C(R7)(R8) wherein R7 and R8, independently of each other, are selected from hydrogen or Ci-4alkyl (and preferably hydrogen or methyl), and B4 is O or C(=0) (and preferably O). In some embodiments of the invention, Z represents:
Z-3 wherein B and B3 represent C(R7)(R8), B2 represents NR9 and and B4 is C(=0).
Otherwise, according to the invention, when X is C(O) and n is 1 , Z is represented by Z-1 wherein B and B2 represent C(R7)(R8); or Z-2 wherein B , B2 and B3 independently represent C(R7)(R8), O or C(=0), wherein only one of B\ B2 and B3 may be O or C(=0); or Z-3 wherein B\ B2, B3 and B4 independently represent C(R7)(R8), O or C(=0), wherein only one of B , B2, B3 and B4 may be O or C(=0); or Z-6a wherein Y represents C(R7)=C(R8); or Z-6c wherein Y represents C2- C4alkylene; or when X is S(0)2, Z-2 wherein B , B2 and B3 independently represent C(R7)(R8). More preferably, when X is C(O), Z is Z-2 wherein B , B2 and B3 independently represent C(R7)(R8) or O, wherein only one of B\ B2 and B3 may be O; or Z-3 wherein B , B2, B3 and B4 independently represent C(R7)(R8) or O, wherein only one of B\ B2, B3 and B4 may be O.
In other embodiments of the invention, when X is C(O) and n is 1 , Z is represented by Z-1 wherein B and B2 represent C(R7)(R8); or Z-2 wherein B , B2 and B3 independently represent C(R7)(R8), O or C(=0), wherein only one of B\ B2 and B3 may be O or C(=0); or Z-3 wherein B\ B2, B3 and B4 independently represent C(R7)(R8), O or C(=0), wherein only one of B , B2, B3 and B4 may be O or C(=0); or Z-6a wherein Y represents C(R7)=C(R8); or Z-6c wherein Y represents C2- C4alkylene; or when X is S(0)2, Z-2 wherein B , B2 and B3 independently represent C(R7)(R8).
In some embodiments of the invention, in Z-3, B , B2, B3 and B4 may independently represent C(R7)(R8), O, S, NR9 or C(=0), wherein only one of B\ B2, B3 and B4 may be a group selected from O, S, NR9 or C(=0).
Preferred Z groups include:
Figure imgf000009_0001
R7 and R8 independently represent hydrogen, halogen, Ci C4alkyl, Ci C4haloalkyl or Ci- C4alkoxy. Preferably, R7 and R8 independently represent hydrogen, fluoro, chloro, methyl, ethyl, difluormethyl, trifluoromethyl or methoxy. More preferably, R7 and R8 independently represent hydrogen, methyl, difluoromethyl, trifluoromethyl or methoxy. Even more preferably, R7 is hydrogen or methyl, and R8 represents hydrogen, methyl, difluoromethyl, trifluoromethyl or methoxy. Still more preferably, R7 and R8 independently represent hydrogen or methyl.
R9 represents hydrogen, Ci-ealkyl, Cs ealkenyl, Cs ealkynyl, Cs ecycloalkyl, Ci ealkoxy, C(0)R10, C(0)OR10, C(O)N(R 0)R11 , S(0)2Rio or S(0)2N(Rio)Rn, wherein Ci-ealkyl, C3-6alkenyl, C3-6alkynyl, C3- 6cycloalkyl and Ci ealkoxy are optionally substituted by halogen or cyano. Preferably, R9 represents hydrogen, Ci-ealkyl, Cs-ealkenyl, Cs-ealkynyl, Cs-ecycloalkyl, Ci-ealkoxy, C(0)R10, C(0)OR ° or C(O)N(R 0)R11 , wherein Ci-6alkyl, Cs ealkenyl, Cs ealkynyl, C3-6cycloalkyl and Ci ealkoxy are optionally substituted by halogen or cyano. More preferably, R9 represents hydrogen, Ci-4alkyl, Ci-4alkoxy, C(0)R10, C(0)OR10, C(O)N(R 0)R11 , S(0)2Rio or S(0)2N(Rio)Rn. Even more preferably, R9 represents hydrogen, Ci-4alkyl, C(0)R10, C(0)OR ° or C(O)N(R 0)R11.
R 0 represents hydrogen, Ci-ealkyl, C3-6cycloalkyl, C3-6cycloalkylCi-2alkyl, Ci-4alkoxyCi-4alkyl, wherein Ci-ealkyl, Cs ecycloalkyl, C3-6cycloalkyl-Ci-2alkyl and Ci-4alkoxy-Ci-4alkyl are optionally substituted by halogen or cyano. Preferably, R 0 represents hydrogen, Ci-4alkyl or Ci-4alkoxyCi-4alkyl.
R represents hydrogen, Ci-4alkyl, Ci-4haloalkyl, Ci-4alkoxy or Ci-4alkoxyCi-4alkyl. Preferably, R represents hydrogen or Ci-4alkyl. In some embodiments according to the invention (in the compounds of Formula (I)):
Preferably, A1 is N or CR\ wherein R is hydrogen or halogen;
A2 is CR2 and R2 is hydrogen; A3 is CR3 and R3 is hydrogen; and A4 is CR4 and R4 is hydrogen; n is 0 or 1 ;
R5 and R6 are hydrogen, or R5 is hydrogen and R6 is methyl, or R5 and R6 are methyl;
X is C(O) or S(0)2;
Z represents Z-2 wherein B and B3 independently represent C(R7)(R8), O, NR9 or C(=0) wherein only one of B and B3 may be a O, NR9 or C(=0), and B2 represents C(R7)(R8); or Z-3 wherein B , B2 and B4 independently represent C(R7)(R8), O, NR9 or C(=0) wherein only one of B\ B2 and B4 may be a O, NR9 or C(=0), and B2 represents C(R7)(R8);
R7 and R8 independently represent hydrogen, methyl, difluoromethyl, trifluoromethyl or methoxy; R9 represents hydrogen, Ci-4alkyl, C(0)R10, C(0)OR ° or C(O)N(R 0)R11.
R 0 represents hydrogen, Ci-4alkyl or Ci-4alkoxyCi-4alkyl; and
R represents hydrogen or Ci-4alkyl. More preferably, A1 represents CR and R is hydrogen; A2 is CR2 and R2 is hydrogen; A3 is CR3 and R3 is hydrogen; and A4 is CR4 and R4 is hydrogen;
n is 1 ;
R5 and R6 are hydrogen;
X is C(O);
Z represents Z-2 wherein B and B3 independently represent C(R7)(R8), O, NR9 or C(=0) wherein only one of B and B3 may be a O, NR9 or C(=0), and B2 represents C(R7)(R8); or Z-3 wherein B , B2 and B4 independently represent C(R7)(R8), O, NR9 or C(=0) wherein only one of B\ B2 and B4 may be a O, NR9 or C(=0), and B2 represents C(R7)(R8);
R7 and R8 independently represent hydrogen, methyl, difluoromethyl, trifluoromethyl or methoxy;
R9 represents hydrogen, Ci-4alkyl, C(0)R10, C(0)OR ° or C(O)N(R 0)R11;
R 0 represents hydrogen, Ci-4alkyl or Ci-4alkoxyCi-4alkyl; and
R represents hydrogen or Ci-4alkyl. In other embodiments according to the invention:
Preferably, A1 represents N or CR1, wherein R is selected from hydrogen or fluoro; A2 is CR2 and R2 is hydrogen; A3 is CR3 and R3 is hydrogen; and A4 is CR4 and R4 is hydrogen;
n is 1 ;
R5 and R6 are hydrogen, or R5 is hydrogen and R6 is methyl, or R5 and R6 are methyl;
Z when X is C(O) represents Z-1 , Z-2, Z-3, Z-5a or Z-5c, or
Z when X is S(0)2 represents Z-2 or Z-3; and
R7 and R8 independently represent hydrogen, chloro, fluoro, methyl, ethyl, difluormethyl, trifluoromethyl or methoxy.
More preferably, A1 represents N or CR1, wherein R is selected from hydrogen or fluoro; A2 is CR2 and R2 is hydrogen; A3 is CR3 and R3 is hydrogen; and A4 is CR4 and R4 is hydrogen;
n is 1 ;
R5 and R6 are hydrogen, or R5 is hydrogen and R6 is methyl, or R5 and R6 are methyl;
X is C(O);
Z represents Z-1 , Z-2, Z-3, Z-6a or Z-6c; and
R7 and R8 independently represent hydrogen, chloro, fluoro, methyl, ethyl, difluormethyl, trifluoromethyl or methoxy. Even more preferably, A1 represents N or CR1, wherein R is hydrogen; A2 is CR2 and R2 is hydrogen, A3 is CR3 and R3 is hydrogen, and A4 is CR4and R4 is hydrogen;
n is 1 ;
R5 and R6 are hydrogen;
X is C(O);
Z represents Z-1 wherein B and B2 represent C(R7)(R8); Z-2 wherein B , B2 and B3 independently represent C(R7)(R8), O or C(=0), wherein only one of B , B2 and B3 may be O or _ _
1 1
C(=0); Z-3 wherein B , B2, B3 and B4 independently represent C(R7)(R8), O or C(=0), wherein only one of B\ B2, B3 and B4 may be O or C(=0); Z-6a wherein Y is C(R7)=(CR8) or Z-6c wherein Y is C2-4alkylene; and
R7 and R8 independently represent hydrogen, methyl, difluoromethyl, trifluoromethyl or methoxy.
Still more preferably, A1 represents CR1 and R is hydrogen, A2 is CR2 and R2 is hydrogen, A3 is CR3 and R3 is hydrogen, and A4 is CR4 and R4 is hydrogen;
n is 1 ;
R5 and R6 are hydrogen;
X is C(O);
Z represents Z-2 wherein B , B2 and B3 independently represent C(R7)(R8) or O, wherein only one of B , B2 and B3 may be O, or Z-3 wherein B , B2, B3 and B4 independently represent C(R7)(R8) or O, wherein only one of B\ B2, B3 and B4 may be O; and
R7 and R8 independently represent hydrogen or methyl.
Further more preferably, A1 represents CR1 and R is hydrogen, A2 is CR2 and R2 is hydrogen, A3 is CR3 and R3 is hydrogen, and A4 is CR4 and R4 is hydrogen;
n is 1 ;
R5 and R6 are hydrogen;
X is C(O);
Z represents Z-2 wherein B , B2 and B3 independently represent C(R7)(R8), or Z-3 wherein B , B2, B3 and B4 independently represent C(R7)(R8); and
R7 and R8 independently represent hydrogen or methyl. In still further embodiments of the invention:
Preferably, A1 is N or CR1 wherein R is hydrogen or fluorine, A2 is CR2 and R2 is hydrogen, A3 is N or CR3 and R3 is hydrogen or fluorine, and A4 is CR4 and R4 is hydrogen;
n is 1 ;
R5 and R6 are hydrogen, or R5 is hydrogen and R6 is methyl, or R5 and R6 are methyl;
X is C(O);
Z represents:
Z-1 wherein B and B2 are C(R7)(R8) and wherein R7 is hydrogen and R8 is hydrogen, methyl, ethyl, difluoromethyl, trifluoromethyl or methoxy;
Z-2 wherein B is C(R7)(R8) wherein R7 and R8 are independently selected from hydrogen and
Ci-4alkyl, B2 is C(R7)(R8) wherein R7 and R8 are independently selected from hydrogen and Ci-4alkyl; and B3 is C(R7)(R8) wherein R7 and R8 are independently selected from hydrogen and Ci-4alkyl, O or C(=0);
Z-3 wherein B is selected from C(R7)(R8) and wherein R7 and R8 are independently selected from hydrogen and Ci-4alkyl, or NR9 wherein R9 is selected from hydrogen or Ci-4alkyl; B2 is selected from C(R7)(R8) wherein R7 and R8 are independently selected from hydrogen and Ci-4alkyl, or NR9 _
12
wherein R9 is selected from C(O)N(R 0)R11 or S(O)2N(R 0)R \ wherein R 0 is selected from hydrogen, or methyl and R is selected from hydrogen, methyl or methoxy; B3 is C(R7)(R8) wherein R7 and R8 are independently selected from hydrogen and Ci-4alkyl; and B4 is selected from C(R7)(R8) wherein R7 and R8 are independently selected from hydrogen and Ci-4alkyl, O or C(=0), wherein only one of B and B2 may be NR9;
Z-5c wherein a is 0 or 1 , and R7 and R8 are independently selected from hydrogen and Ci-
4alkyl;
Z-5g wherein a is 0 or 1 , and R7 and R8 are independently selected from hydrogen and Ci- 4alkyl; or
Z-6c wherein Y is C2-3alkylene, and R7 and R8 are independently selected from hydrogen and
Ci-4alkyl.
More preferably, A1 is CR and R is hydrogen, A2 is CR2 and R2 is hydrogen, A3 is CR3 and R3 is hydrogen, and A4 is CR4 and R4 is hydrogen;
n is 1 ;
R5 and R6 are hydrogen;
X is C(O);
Z represents:
Z-1 wherein B and B2 are C(R7)(R8) and wherein R7 is hydrogen and R8 is hydrogen, methyl, difluoromethyl, trifluoromethyl or methoxy;
Z-2 wherein B is C(R7)(R8) wherein R7 and R8 are independently selected from hydrogen and methyl, B2 is C(R7)(R8) wherein R7 and R8 are independently selected from hydrogen and methyl; and B3 is C(R7)(R8) wherein R7 and R8 are independently selected from hydrogen and methyl, O or C(=0);
Z-3 wherein B is selected from C(R7)(R8) and wherein R7 and R8 are independently selected from hydrogen and methyl, or NR9 wherein R9 is selected from hydrogen or Ci-4alkyl; B2 is selected from C(R7)(R8) wherein R7 and R8 are independently selected from hydrogen and methyl, or NR9 wherein R9 is selected from C(O)N(R 0)R11 or S(O)2N(R 0)R \ wherein R 0 is selected from hydrogen or methyl and R is selected from hydrogen, methyl or methoxy; B3 is C(R7)(R8) wherein R7 and R8 are independently selected from hydrogen and methyl; and B4 is selected from C(R7)(R8) wherein R7 and R8 are independently selected from hydrogen and methyl, O or C(=0), wherein only one of B and B2 may be NR9;
Z-5c wherein a is 0, and R7 and R8 are independently selected from hydrogen and methyl; Z-5g wherein a is 0, and R7 and R8 are independently selected from hydrogen and methyl; or Z-6c wherein Y is C2-3alkylene, and R7 and R8 are independently selected from hydrogen and methyl.
Even more preferably, A1 is CR1 and R is hydrogen, A2 is CR2 and R2 is hydrogen, A3 is CR3 and R3 is hydrogen, and A4 is CR4 and R4 is hydrogen;
n is 1 ;
R5 and R6 are hydrogen;
X is C(O); Z represents:
Z-1 wherein B and B2 are C(R7)(R8) and wherein R7 is hydrogen and R8 is hydrogen, methyl, difluoromethyl or trifluoromethyl;
Z-2 wherein B is C(R7)(R8) wherein R7 and R8 are independently selected from hydrogen and methyl, B2 is C(R7)(R8) wherein R7 and R8 are independently selected from hydrogen and methyl; and B3 is C(R7)(R8) wherein R7 and R8 are independently selected from hydrogen and methyl, O or C(=0);
Z-3 wherein B is selected from C(R7)(R8) and wherein R7 and R8 are independently selected from hydrogen and methyl, or NR9 wherein R9 is selected from hydrogen or methyl; B2 is selected from C(R7)(R8) wherein R7 and R8 are independently selected from hydrogen and methyl, or NR9 wherein R9 is selected from C(O)N(R 0)R11 or S(O)2N(R 0)R \ wherein R 0 is selected from hydrogen or methyl and R is selected from hydrogen, methyl or methoxy; B3 is C(R7)(R8) wherein R7 and R8 are independently selected from hydrogen and methyl; and B4 is selected from C(R7)(R8) wherein R7 and R8 are independently selected from hydrogen and methyl, or C(=0), wherein only one of B and B2 may be NR9;
Z-5c wherein a is 0, and R7 and R8 are independently selected from hydrogen and methyl;
Z-5g wherein a is 0, and R7 and R8 are independently selected from hydrogen and methyl; or Z-6c wherein Y is ethylene, and R7 and R8 are independently selected from hydrogen and methyl. Preferably, the compound according to Formula (I) is selected from a compound A-1 to A-70 described in Table A (below), a compound B-1 to B-4 described in Table B (below), a compound C-1 to C-3 described in Table C (below), or compound D-1 described in Table D (below).
The compounds of the present invention may be enantiomers of the compound of Formula (I) as represented b a Formula (l-a) or a Formula (l-b), wherein n is 1 , and R5 and R6 are different.
Figure imgf000014_0001
(l-a) (l-b)
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, Z (X, Y, a, B\ B2, B3, B4, B5), R\ R2, R3, R4, R5, R6, R7, R8, R9, R 0 and R , 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, Z (X, Y, a, B\ B2, B3, B4, B5), R\ R2, R3, R4, R5, R6, R7, R8, R9, R 0 and R as represented in Tables 1 a to 1d below, or the compounds A-1 to A-70 described in Table A (below), the compounds B-1 to B-4 described in Table B (below), the compounds C-1 to C-3 described in Table C (below), or compound D-1 described in Table D (below).
Figure imgf000015_0001
(l-l) (l-ll)
Compounds of the present invention can be made as shown in the following schemes 1 to 10, in which, unless otherwise stated, the definition of each variable is as defined above for a compound of formula (I). Compounds of formula (I) can be prepared from compounds of formula (III), wherein X is F, CI,
Br, I, or OSCteMe, via treatment with compounds of formula (II), in the presence of a base (e.g. lithium hexamethyldisilylazide, n-butyllithium, CS2CO3, CSF, K2CO3 or NaH) in a suitable solvent (e.g. dimethylformamide, acetone or tetrahydrofuran) at a temperature between -78°C and 25°C.
Additionally, some reactions might only proceed at higher temperature and/or in the presence of a catalyst system such as Cul/dimethylethylenediamine or Pd(OAc)2/Xantphos. For related examples, see: WO 2004/087646; WO 2013/132253; Garcia, M. ef al Org. Biomol. Chem. 2004, 11, 1633;
Guyonner, M. and Baudoin, O. Org. Lett. 2012, 14, 398; Philipps, D. P. ef al. Tetrahedron Lett. 2009,
50, 7293. This reaction is shown in Scheme 1.
Figure imgf000015_0002
(II) (I)
Scheme 1 Alternatively, compounds of formula (I), or compounds of formula (XII), can be prepared from compounds of formula (IV) or (IVa), respectively, by treatment with trifluoroacetic anhydride in the presence of a base (e.g. 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 2.
Figure imgf000016_0001
Scheme 2
Compounds of formula (IV) and (IVa) can be prepared from compounds of formula (V) and (Va), respectively, by treating them 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 65°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 3.
Figure imgf000017_0001
Figure imgf000017_0002
Scheme 3
Compounds of formula (V) and (Va) can be prepared from compounds of formula (VI) and (Via), respectively, wherein V 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 (e.g. 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 4.
Figure imgf000017_0003
Scheme 4
Compounds of formula (VI), wherein V is Br or I, or CN (also corresponding to compound (V)), can be prepared from compounds of formula (VIII), wherein X is F, CI, Br, I, or OSCteMe, via treatment with compounds of formula (II), in the presence of a base (e.g. lithium hexamethyldisilylazide, n- butyllithium, CS2CO3, CSF, K2CO3 or NaH) in a suitable solvent (e.g. dimethylformamide, acetone or tetrahydrofuran) at a temperature between -78°C and 25°C. Additionally, some reactions might only proceed at higher temperature and/or in the presence of a catalyst system such as Cul/dimethylethylenediamine or Pd(OAc)2 Xantphos. For related examples, see: WO 2004/087646; WO 2013/132253; Garcia, M. et al Org. Biomol. Chem. 2004, 11, 1633; Guyonner, M. and Baudoin, O. Org. Lett. 2012, 14, 398; Philipps, D. P. ei al. Tetrahedron Lett. 2009, 50, 7293. This reaction is shown in Scheme 5.
Figure imgf000018_0001
Scheme 5
Compounds of formula (VII) (i.e., compounds of Formula (VI) wherein R5 is H) wherein V is Br, I, or CN, can be prepared from carbonyl compounds of formula (IX), via treatment with compounds of formula (II) in the presence of a base, such as triethylamine, in a suitable solvent (eg, methanol or ethanol) at a temperature between 0°C and 100°C; followed by the addition of a reducing reagent (e.g. NaBhU or NaBh CN). For related examples, see: WO 2013/071232 and WO 2013/066838. This reaction is shown in Scheme 6.
Figure imgf000018_0002
(II) (IX) (VII)
Scheme 6
Compounds of formula (VIII), wherein V is Br, I, or CN and X is CI or Br, are either commercially available or can be prepared from compounds of formula (Via), by treatment with a halogen source, (eg, N-bromosuccimide (NBS) or N-chlorosuccimide (NCS)) and a radical initiator, such as (PhC02)2 or azobisisobutyronitrile (AIBN), in the presence of ultraviolet light, in a suitable solvent, such as tetrachloromethane, at temperatures between 55°C and 100°C. For related examples, see Liu, S. ei al Syntheis (2001 ), 14, 2078 and Kompella, A. et al Org. Proc. Res. Dev. (2012), 16, 1794. This reaction is shown in Scheme 7. Compounds of formula (Via) are commercially available. Λ„
Figure imgf000019_0001
(Via)
(VIII)
Scheme 7
Alternatively, compounds of formula (VIII), wherein X is CI, Br, I, or OSCteMe are either commercially available or can be prepared from compounds of formula (X), wherein V is Br, I or CN, by treatment with a halogen source (eg, CBr4, CCU or ) in the presence of triphenylphosphine, or with methanesulfonyl chloride (CISChMe), in a suitable solvent, (eg, dichloromethane or 1 ,2- dichloroethane) at a temperature between 0°C and 80°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 (X) are commercially available. This reaction is shown in Scheme 8.
Figure imgf000019_0002
(X) (VIII)
Scheme 8
Compounds of formula (IX), wherein V is Br, I, or CN are either commercially available or can be prepared from compounds of formula (XI) (compound (X) when R5 is H), by treatment with an oxidizing reagent (eg, KMnC or MnCte) in a suitable solvent, (eg, dioxane or dichloromethane) at a temperature between 25°C and 1 10°C. For related examples, see WO 2003/0087940 and WO 2008/104306. Compounds of formula (XI) are commercially available. This reaction is shown in Scheme 9.
Figure imgf000019_0003
(XI) (IX)
Scheme 9 Compounds of formula (III) wherein X is CI or Br, can be prepared from compounds of formula (XII) by treatment with a halogen source (eg, N-bromosuccimide (NBS) or N-chlorosuccimide (NCS)) and a radical initiator (eg, (PhC02)2 or azobisisobutyronitrile (AIBN)) in a suitable solvent, such as tetrachloromethane, at temperatures between 55° and 100°C in the presence of ultraviolet light. For related examples, see Liu, S. ei al Synthesis (2001 ), 14, 2078 and Kompella, A. ei al Org. Proc. Res. Dev. 2012), 16, 1794. This reaction is shown in Scheme 10.
Figure imgf000020_0001
(XII) (III)
Scheme 10 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 nonvolatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound. Granular formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins. Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.
Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates. Encapsulated droplets are typically 1 to 50 microns in diameter. The enclosed liquid typically constitutes 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound. Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores. Granules typically range from 1 millimetre to 1 centimetre and preferably 1 to 2 millimetres in diameter. Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene- butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
Other useful formulations for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurised sprayers, wherein the active ingredient is dispersed in finely-divided form as a result of vaporisation of a low boiling dispersant solvent carrier, may also be used.
Suitable agricultural adjuvants and carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to those skilled in the art.
Liquid carriers that can be employed include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, Ν,Ν-dimethyl formamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidinone, ethyl acetate, 2-ethyl hexanol, ethylene carbonate, 1 , 1 ,1-trichloroethane, 2-heptanone, alpha pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropyl benzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octyl amine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol, glycerine and N-methyl-2-pyrrolidinone. Water is generally the carrier of choice for the dilution of concentrates. Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller's earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.
A broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application. These agents, when used, normally comprise from 0.1 % to 15% by weight of the formulation. They can be anionic, cationic, non-ionic or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes. Typical surface active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub. 18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C.sub. 16 ethoxylate; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.
Other adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, anti-foaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and sticking agents.
In addition, further, other biocidally active ingredients or compositions may be combined with the compositions of the invention and used in the methods of the invention and applied simultaneously or sequentially with the compositions of the invention. When applied simultaneously, these further active ingredients may be formulated together with the compositions of the invention or mixed in, for example, the spray tank. These further biocidally active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.
Pesticidal agents are referred to herein using their common name are known, for example, from "The Pesticide Manual", 15th Ed., British Crop Protection Council 2009.
In addition, the compositions of the invention may also be applied with one or more system ically acquired resistance inducers ("SAR" inducer). SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.
The compounds of formula (I) are normally used in the form of agrochemical compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g. fertilizers or micronutrient donors or other preparations, which influence the growth of plants. They can also be selective herbicides or non- selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
The compounds of formula (I) may be used in the form of (fungicidal) compositions for controlling or protecting against phytopathogenic microorganisms, comprising as active ingredient at least one compound of formula (I) or of at least one preferred individual compound as defined herein, in free form or in agrochemically usable salt form, and at least one of the above-mentioned adjuvants.
The invention therefore provides a composition, preferably a fungicidal composition, comprising at least one compound formula (I) an agriculturally acceptable carrier and optionally an adjuvant. An agricultural acceptable carrier is for example a carrier that is suitable for agricultural use. Agricultural carriers are well known in the art. Preferably said composition may comprise at least one or more 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,N - dimethyl-5-p-tolylimidazole-1-sulfonamide, N-allyl-4, 5,- dimethyl-2-trimethylsilylthiophene-3-carboxamide, N- (l-cyano-1 , 2-d i m ethyl p ropy I )-2- (2, 4- dichlorophenoxy) propionamide, N- (2-methoxy-5-pyridyl)-cyclopropane carboxamide, (.+-.)-cis-1-(4- chlorophenyl)-2-(1 H-1 ,2,4-triazol-1-yl)-cycloheptanol, 2-(1-iert-butyl)-1-(2-chlorophenyl)-3-(1 ,2,4- triazol-1-yl)-propan-2-ol, 2 6'-dibromo-2-methyl-4-trifluoromethoxy-4'-trifluoromethyl-1 ,3-thiazole- 5- carboxanilide, 1-imidazolyl-1-(4'-chlorophenoxy)-3,3-dimethylbutan-2-one, methyl (E)-2-[2-[6-(2- cyanophenoxy)pyrimidin-4-yloxy]phenyl]3-methoxyacrylate, methyl (E)-2-[2-[6-(2- thioamidophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[6-(2- fluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[6-(2,6- difluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacryla te, methyl (E)-2-[2-[3-(pyrimidin-2- yloxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[3-(5-methylpyrimidin-2-yloxy)- phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[3-(phenyl-sulphonyloxy)phenoxy]phenyl-3- methoxyacrylate, methyl (E)-2-[2-[3-(4-nitrophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2- [2-phenoxyphenyl]-3-methoxyacrylate, methyl (E)-2-[2-(3,5-dimethyl-benzoyl)pyrrol-1-yl]-3- methoxyacrylate, methyl (E)-2-[2-(3-methoxyphenoxy)phenyl]-3-methoxyacrylate, methyl (E)-2[2-(2- phenylethen-1-yl)-phenyl]-3-methoxyacrylate, methyl (E)-2-[2-(3,5-dichlorophenoxy)pyridin-3-yl]-3- methoxyacrylate, methyl (E)-2-(2-(3-(1 , 1 ,2,2-tetrafluoroethoxy)phenoxy)phenyl)-3-methoxyacrylate, methyl (E)-2-(2-[3-(alpha-hydroxybenzyl)phenoxy]phenyl)-3-methoxyacrylate, methyl (E)-2-(2-(4- phenoxypyridin-2-yloxy)phenyl)-3-methoxyacrylate, methyl (E)-2-[2-(3-n-propyloxy-phenoxy)phenyl]3- methoxyacrylate, methyl (E)-2-[2-(3-isopropyloxyphenoxy)phenyl]-3-methoxyacrylate, methyl (E)-2-[2- [3-(2-fluorophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-(3-ethoxyphenoxy)phenyl]-3- methoxyacrylate, methyl (E)-2-[2-(4-ieri-butyl-pyridin-2-yloxy)phenyl]-3-methoxyacrylate, methyl (E)-2- [2-[3-(3-cyanophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[(3-methyl-pyridin-2- yloxymethyl)phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[6-(2-methyl-phenoxy)pyrimidin-4- yloxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-(5-bromo-pyridin-2-yloxymethyl)phenyl]-3- methoxyacrylate, methyl (E)-2-[2-(3-(3-iodopyridin-2-yloxy)phenoxy)phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[6-(2-chloropyridin-3-yloxy)pyrimidin-4-yloxy]phenyl]-3-methoxyac rylate, methyl (E),(E)-2-[2- (5,6-dimethylpyrazin-2-ylmethyloximinomethyl)phenyl]-3-methox yacrylate, methyl (E)-2-{2-[6-(6- methylpyridin-2-yloxy)pyrimidin-4-yloxy]phenyl}-3-methoxy-a crylate, methyl (E),(E)-2-{ 2-(3- methoxyphenyl)methyloximinomethyl]-phenyl}-3-methoxyacrylate, methyl (E)-2-{2-(6-(2- azidophenoxy)-pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate, methyl (E),(E)-2-{2-[6-phenylpyrimidin-4- yl)-methyloximinomethyl]phenyl}-3-methox yacrylate, methyl (E),(E)-2-{2-[(4-chlorophenyl)- methyloximinomethyl]-phenyl}-3-methoxyacryl ate, methyl (E)-2-{2-[6-(2-n-propylphenoxy)-1 ,3,5- triazin-4-yloxy]phenyl}-3-methoxyacr ylate, methyl (E),(E)-2-{2-[(3- nitrophenyl)methyloximinomethyl]phenyl}-3-methoxyacrylate, 3-chloro-7-(2-aza-2,7,7-trimethyl-oct-3- en-5-ine), 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide, 3-iodo-2-propinyl alcohol, 4- chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenyl ethylcarbamate, 2,3,3-triiodoallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propinyl n-butylcarbamate, 3-iodo-2-propinyl n-hexylcarbamate, 3-iodo-2-propinyl cyclohexyl-carbamate, 3-iodo-2-propinyl phenylcarbamate; phenol derivatives, such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl- 4-chlorophenol, phenoxyethanol, dichlorophene, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2- benzyl-4-chlorophenol, 5-hydroxy-2(5H)-furanone; 4,5-dichlorodithiazolinone, 4,5-benzodithiazolinone, 4,5-trimethylenedithiazolinone, 4,5-dichloro-(3H)-1 ,2-dithiol-3-one, 3,5-dimethyl-tetrahydro-1 ,3,5- thiadiazine-2-thione, N-(2-p-chlorobenzoylethyl)-hexaminium chloride, acibenzolar, acypetacs, alanycarb, albendazole, aldimorph, allicin, allyl alcohol, ametoctradin, amisulbrom, amobam, ampropylfos, anilazine, asomate, aureofungin, azaconazole, azafendin, azithiram, azoxystrobin, barium polysulfide, benalaxyl, benalaxyl-M, benodanil, benomyl, benquinox, bentaluron, benthiavalicarb, benthiazole, benzalkonium chloride, benzamacril, benzamorf, benzohydroxamic acid, benzovindiflupyr, berberine, bethoxazin, biloxazol, binapacryl, biphenyl, bitertanol, bithionol, bixafen, blasticidin-S, boscalid, bromothalonil, bromuconazole, bupirimate, buthiobate, butylamine calcium polysulfide, captafol, captan, carbamorph, carbendazim, carbendazim chlorhydrate, carboxin, carpropamid, carvone, CGA41396, CGA41397, chinomethionate, chitosan, chlobenthiazone, chloraniformethan, chloranil, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlorozolinate, chlozolinate, climbazole, clotrimazole, clozylacon, copper containing compounds such as copper acetate, copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper oxyquinolate, copper silicate, copper sulphate, copper tallate, copper zinc chromate and Bordeaux mixture, cresol, cufraneb, cuprobam, cuprous oxide, cyazofamid, cyclafuramid, cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazole, cyprodinil, dazomet, debacarb, decafentin, dehydroacetic acid, di-2-pyridyl disulphide 1 , 1 '-dioxide, dichlofluanid, diclomezine, dichlone, dicloran, dichlorophen, dichlozoline, diclobutrazol, diclocymet, diethofencarb, difenoconazole, difenzoquat, diflumetorim, O, O-di-iso-propyl-S-benzyl thiophosphate, dimefluazole, dimetachlone, dimetconazole, dimethomorph, dimethirimol, diniconazole, diniconazole-M, dinobuton, dinocap, dinocton, dinopenton, dinosulfon, dinoterbon, diphenylamine, dipyrithione, disulfiram, ditalimfos, dithianon, dithioether, dodecyl dimethyl ammonium chloride, dodemorph, dodicin, dodine, doguadine, drazoxolon, edifenphos, enestroburin, epoxiconazole, etaconazole, etem, ethaboxam, ethirimol, ethoxyquin, ethilicin, ethyl (Z)-N-benzyl-N ([methyl (methyl-thioethylideneamino- oxycarbonyl) amino] thio)^-alaninate, etridiazole, famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenitropan, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, flupicolide, fluopyram, fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutanil, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl, fuberidazole, furalaxyl, furametpyr, furcarbanil, furconazole, furfural, furmecyclox, furophanate, glyodin, griseofulvin, guazatine, halacrinate, hexa chlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexylthiofos, hydrargaphen, hydroxyisoxazole, hymexazole, imazalil, imazalil sulphate, imibenconazole, iminoctadine, iminoctadine triacetate, inezin, iodocarb, ipconazole, ipfentrifluconazole, iprobenfos, iprodione, iprovalicarb, isopropanyl butyl carbamate, isoprothiolane, isopyrazam, isotianil, isovaledione, izopamfos, kasugamycin, kresoxim- methyl, LY186054, LY211795, 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 96/11945, WO 93/19053, WO 93/25543, EP 0 626 375, EP 0 382 173, WO 94/19334, EP 0 382 173, and EP 0 503 538. The compounds of the invention may be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.
The compounds of the invention may be used in combination with terpene alkaloids, for example those described in International Patent Application Publication Numbers WO 95/19363 or WO 04/72086, particularly the compounds disclosed therein.
Other examples of such biologically active compounds that the compounds of the invention may be used in combination with include but are not restricted to the following:
Organophosphates: acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, bromophos, bromophos-ethyl, cadusafos, chlorethoxyphos, chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demeton-S-methyl, demeton-S-methyl sulphone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosthiazate, heptenophos, isazophos, isothioate, isoxathion, malathion, methacriphos, methamidophos, methidathion, methyl- parathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, paraoxon, parathion, parathion-methyl, phenthoate, phosalone, phosfolan, phosphocarb, phosmet, phosphamidon, phorate, phoxim, pirimiphos, pirimiphos- methyl, profenofos, propaphos, proetamphos, prothiofos, pyraclofos, pyridapenthion, quinalphos, sulprophos, temephos, terbufos, tebupirimfos, tetrachlorvinphos, thimeton, triazophos, trichlorfon, vamidothion.
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-1111 , R- 5 195,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.
0 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.
5
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 compound0 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 of5 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 the0 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 by5 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 drenching0 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 ingre- dients 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 1a (below) discloses 46 combinations (compounds 1a.001 to 1a.046) of A1 , A2, A3, A4,
R5, R7 and R8 substituents in accordance with compounds as defined for Formula (T-1 ). Formula (T-1 ) corresponds to Formula (I) as defined for the present invention.
Figure imgf000036_0001
Each of Tables 2a to 22a (which follow Table 1a) make available 46 additional individual compounds of the formula (T-1 ) in which Z and R6 are as specifically defined in Tables 2a to 22a (Formulae T-1a.2 to T-1a.22), which refer to Table 1a wherein A1 , A2, A3, A4, R5, R7 and R8 are specifically defined. Table 1a:
Compound
A1 A2 A3 A4 R5 R7 R8
no.
1a.001 C-H C-H C-H C-H H H H
1a.002 C-H C-H C-H C-H H H CH3
1a.003 C-H C-H C-H C-H H CH3 CH3
1a.004 C-H C-H C-H C-H CH3 H H
1a.005 C-H C-H C-H C-H CH3 H CH3
1a.006 C-H C-H C-H C-H CH3 CH3 CH3
1a.007 C-F C-H C-H C-H H H H a.008 C-F C-H C-H C-H H H CH3a.009 C-F C-H C-H C-H H CH3 CH3a.010 C-F C-H C-H C-H CH3 H Ha.011 C-F C-H C-H C-H CH3 H CH3a.012 C-F C-H C-H C-H CH3 CH3 CH3a.013 C-CHs C-H C-H C-H H H Ha.014 C-CHs C-H C-H C-H H H CH3a.015 C-CHs C-H C-H C-H H CH3 CH3a.016 C-CHs C-H C-H C-H CH3 H Ha.017 N C-H C-H C-H H H Ha.018 N C-H C-H C-H H H CH3a.019 N C-H C-H C-H H CH3 CH3a.020 N C-H C-H C-H CH3 H Ha.021 N C-H C-H C-H CH3 H CH3a.022 N C-H C-H C-H CH3 CH3 CH3a.023 C-CI C-H C-H C-H H H Ha.024 C-CI C-H C-H C-H H H CH3a.025 C-CI C-H C-H C-H H CH3 CH3a.026 C-CI C-H C-H C-H CH3 H Ha.027 C-OCH3 C-H C-H C-H H H Ha.028 C-OCH3 C-H C-H C-H H H CH3a.029 C-OCH3 C-H C-H C-H H CH3 CH3a.030 C-OCH3 C-H C-H C-H CH3 H Ha.031 C-CF3 C-H C-H C-H H H Ha.032 C-CF3 C-H C-H C-H H H CH3a.033 C-CF3 C-H C-H C-H H CH3 CH3a.034 C-CF3 C-H C-H C-H CH3 H Ha.035 C-H C-H C-F C-H H H Ha.036 C-H C-H C-F C-H H H CH3a.037 C-H C-H C-F C-H H CH3 CH3a.038 C-H C-H C-F C-H CH3 H Ha.039 C-H C-H N C-H H H Ha.040 C-H C-H N C-H H H CH3a.041 C-H C-H N C-H H CH3 CH3a.042 C-H C-H N C-H CH3 H Ha.043 N N C-H C-H H H Ha.044 N N C-H C-H H H CH3a.045 N N C-H C-H H CH3 CH3a.046 N N C-H C-H CH3 H H Table 2a: This table discloses compounds 2a.001 to 2a.046 of the formula (T-1a.2), which is a compound of formula (I) wherein R6 is H and A1 , A2, A3, A4, R5, R7 and R8 have the specific meanings given in the Table 1a.
Figure imgf000038_0001
Table 3a: This table discloses compounds 3a.001 to 3a.046 of the formula (T-1a.3), which is a compound of formula (I) wherein R6 is H and A1 , A2, A3, A4, R5, R7 and R8 have the specific meanings iven in the Table 1a.
Figure imgf000038_0002
Table 4a: This table discloses compounds 4a.001 to 4a.046 of the formula (T-1a.4), which is a compound of formula (I) wherein R6 is H and A1 , A2, A3, A4, R5, R7 and R8 have the specific meanings given in the Table 1a.
Figure imgf000038_0003
Table 5a: This table discloses compounds 5a.001 to 5a.046 of the formula (T-1a.5), which is a compound of formula (I) wherein R6 is H and A1 , A2, A3, A4, R5, R7 and R8 have the specific meanings given in the Table 1a.
Figure imgf000038_0004
Table 6a: This table discloses compounds 6a.001 to 6a.046 of the formula (T-1a.6), which is a compound of formula (I) wherein R6 is H and A1 , A2, A3, A4, R5, R7 and R8 have the specific meanings given in the Table 1a.
Figure imgf000039_0001
Table 7a: This table discloses compounds 7a.001 to 7a.046 of the formula (T-1a.7), which is a compound of formula (I) wherein R6 is H and A1 , A2, A3, A4, R5, R7 and R8 have the specific meanings given in the Table 1a.
Figure imgf000039_0002
Table 8a: This table discloses compounds 8a.001 to 8a.046 of the formula (T-1a.8), which is a compound of formula (I) wherein R6 is H and A1 , A2, A3, A4, R5, R7 and R8 have the specific meanings given in the Table 1a.
Figure imgf000039_0003
Table 9a: This table discloses compounds 9a.001 to 9a.046 of the formula (T-1a.9), which is a compound of formula (I) wherein R6 is H and A1 , A2, A3, A4, R5, R7 and R8 have the specific meanings given in the Table 1a.
Figure imgf000039_0004
Table 10a: This table discloses compounds 10a.001 to 10a.046 of the formula (T-1a.10), which is a compound of formula (I) wherein R6 is H and A1 , A2, A3, A4, R5, R7 and R8 have the specific meanings given in the Table 1a.
Figure imgf000040_0001
Table 1 1a: This table discloses compounds 1 1a.001 to 1 1a.046 of the formula (T-1a.1 1 ), which is a compound of formula (I) wherein R6 is H and A1, A2, A3, A4, R5, R7 and R8 have the specific meanin s given in the Table 1a.
Figure imgf000040_0002
Table 12a: This table discloses compounds 12a.001 to 12a.046 of the formula (T-1a.12), which is a compound of formula (I) wherein R6 is H and A1 , A2, A3, A4, R5, R7 and R8 have the specific meanings given in the Table 1a.
Figure imgf000040_0003
Table 13a: This table discloses compounds 13a.001 to 13a.046 of the formula (T-1a.13), which is a compound of formula (I) wherein R6 is H and A1, A2, A3, A4, R5, R7 and R8 have the specific meanin s given in the Table 1a.
Figure imgf000040_0004
Table 14a: This table discloses compounds 14a.001 to 14a.046 of the formula (T-1a.14), which is a compound of formula (I) wherein R6 is H and A1 , A2, A3, A4, R5, R7 and R8 have the specific meanings given in the Table 1.
Figure imgf000041_0001
Table 15a: This table discloses compounds 15a.001 to 15a.046 of the formula (T-1a.15), which is a compound of formula (I) wherein R6 is H and A1 , A2, A3, A4, R5, R7 and R8 have the specific meanin s given in the Table 1a.
Figure imgf000041_0002
Table 16a: This table discloses compounds 16a.001 to 16a.046 of the formula (T-1a.16), which is a compound of formula (I) wherein R6 is H and A1, A2, A3, A4, R5, R7 and R8 have the specific meanin s given in the Table 1a.
Figure imgf000041_0003
Table 17a: This table discloses compounds 17a.001 to 17a.046 of the formula (T-1a.17), which is a compound of formula (I) wherein R6 is H and A1 , A2, A3, A4, R5, R7 and R8 have the specific meanings given in the Table 1a.
Figure imgf000041_0004
Table 18a: This table discloses compounds 18a.001 to 18a.046 of the formula (T-1a.18), which is a compound of formula (I) wherein R6 is H and A1, A2, A3, A4, R5, R7 and R8 have the specific meanings given in the Table 1 a.
Figure imgf000042_0001
Table 19a: This table discloses compounds 19a.001 to 19a.046 of the formula (T-1a.19), which is a compound of formula (I) wherein R6 is H and A1 , A2, A3, A4, R5, R7 and R8 have the specific meanin s given in the Table 1a.
Figure imgf000042_0002
Table 20a: This table discloses compounds 20a.001 to 20a.046 of the formula (T-1a.20), which is a compound of formula (I) wherein R6 is H and A1 , A2, A3, A4, R5, R7 and R8 have the specific meanin s given in the Table 1a.
Figure imgf000042_0003
Table 21 a: This table discloses compounds 21a.001 to 21 a.046 of the formula (T-1a.21 ), which is a compound of formula (I) wherein R6 is H and A1 , A2, A3, A4, R5, R7 and R8 have the specific meanin s given in the Table 1a.
Figure imgf000042_0004
Table 22a: This table discloses compounds 22a.001 to 22a.046 of the formula (T-1a.22), which is a compound of formula (I) wherein R6 is H and A1, A2, A3, A4, R5, R7 and R8 have the specific meanings given in the Table 1a.
Figure imgf000043_0001
Table 1b (below) discloses 138 combinations (compounds 1b.001 to 1b.138) of A1, A2, A3, A4, R5, R7, R8and R9 substituents in accordance with compounds as defined for Formula (T-1), wherein heterocycle Z contains a NR9 ring member. Formula (T-1) corresponds to Formula (I) as defined for the present invention.
Figure imgf000043_0002
Each of Tables 2b to 4b (which follow Table 1b) make available 138 additional individual compounds of the formula (T-1) in which Z and R6 are as specifically defined in Tables 2b to 4b (Formulae T-1b.2 to T-1b.4), which refer to Table 1b wherein A1, A2, A3, A4, R5, R7, R8 and R9 are specifically defined.
Table 1b:
Figure imgf000043_0003
Table 2b: This table discloses compounds 2b.001 to 2b.138 of the formula (T-1b.2), which is a compound of formula (I) wherein R6 is H and A1, A2, A3, A4, R5, R7, R8 and R9 have the specific meanings given in the Table 1b.
Figure imgf000044_0001
Table 3b: This table discloses compounds 3b.001 to 3b.138 of the formula (T-1b.3), which is a compound of formula (I) wherein R6 is H and A1, A2, A3, A4, R5, R7, R8 and R9 have the specific meanin s given in the Table 1b.
Figure imgf000044_0002
Table 4b: This table discloses compounds 4b.001 to 4b.138 of the formula (T-1b.4), which is a compound of formula (I) wherein R6 is H and A1, A2, A3, A4, R5, R7, R8 and R9 have the specific meanin s given in the Table 1b.
Figure imgf000044_0003
Table 1c (below) discloses 690 combinations (compounds 1c.001 to 1c.690) of A1, A2, A3, A4, R5, R7, R8, R9, R0and R substituents in accordance with compounds as defined for Formula (T-1), wherein heterocycle Z contains a NR9 ring member. Formula (T-1) corresponds to Formula (I) as defined for the present invention.
Figure imgf000044_0004
Table 2c (which follows Table 1c) makes available 690 additional individual compounds of the formula (T-1) in which Z and R6 are as specifically defined in Table 2c (Formula T-1c.2), which refers to Table 1c wherein A1, A2, A3, A4, R5, R7, R8, R9, R0and R are specifically defined. Table 1c:
Figure imgf000045_0001
Table 2c: This table discloses compounds 2c.001 to 2c.690 of the formula (T-1c.2), which is a compound of formula (I) wherein R6 is H and A1, A2, A3, A4, R5, R7, R8, R9, R 0 and R have the s ecific meanings given in the Table 1c.
Figure imgf000046_0001
Table 1d (below) discloses 30 combinations (compounds 1d.001 to 1d.030) of A1, A2, A3, A4, R7 and R8 substituents in accordance with compounds as defined for Formula (T-2). Formula (T-2) corresponds to Formula (I) as defined for the present invention.
Figure imgf000046_0002
(T-2)
Each of Tables 2d to 13d (which follow Table 1d) make available 30 additional individual compounds of the formula (T-2) in which Z is as specifically defined in Tables 2d to 13d (Formulae T- 2d.2 to T-2d.13), which refer to Table 1d wherein A1, A2, A3, A4, R7 and R8 are specifically defined.
Table 1d:
Compound
A1 A2 A3 A4 R7 R8
no.
1d.001 C-H C-H C-H C-H H H
1d.002 C-H C-H C-H C-H H CH3
1d.003 C-H C-H C-H C-H CH3 CH3
1d.004 C-F C-H C-H C-H H H
1d.005 C-F C-H C-H C-H H CH3
1d.006 C-F C-H C-H C-H CH3 CH3
1d.007 C-CHs C-H C-H C-H H H
1d.008 C-CHs C-H C-H C-H H CH3
1d.009 C-CHs C-H C-H C-H CH3 CH3
1d.010 N C-H C-H C-H H H
1d.011 N C-H C-H C-H H CH3 1d.012 N C-H C-H C-H CH3 CH3
1d.013 C-CI C-H C-H C-H H H
1d.014 C-CI C-H C-H C-H H CH3
1d.015 C-CI C-H C-H C-H CH3 CH3
1d.016 C-OCH3 C-H C-H C-H H H
1d.017 C-OCH3 C-H C-H C-H H CH3
1d.018 C-OCH3 C-H C-H C-H CH3 CH3
1d.019 C-CF3 C-H C-H C-H H H
1d.020 C-CF3 C-H C-H C-H H CH3
1d.021 C-CF3 C-H C-H C-H CH3 CH3
1d.022 C-H C-H C-F C-H H H
1d.023 C-H C-H C-F C-H H CH3
1d.024 C-H C-H C-F C-H CH3 CH3
1d.025 C-H C-H N C-H H H
1d.026 C-H C-H N C-H H CH3
1d.027 C-H C-H N C-H CH3 CH3
1d.028 N N C-H C-H H H
1d.029 N N C-H C-H H CH3
1d.030 N N C-H C-H CH3 CH3
Table 2d: This table discloses compounds 2d.001 to 2d.030 of the formula (T-2d.2), which is a compound of formula (I) wherein A1, A2, A3, A4, R7 and R8 have the specific meanings given in the Table 1d.
Figure imgf000047_0001
Table 3d: This table discloses compounds 3d.001 to 3d.030 of the formula (T-2d.3), which is a compound of formula (I) wherein A1, A2, A3, A4, R7 and R8 have the specific meanings given in the Table 1d.
Figure imgf000048_0001
Table 4d: This table discloses compounds 4d.001 to 4d.030 of the formula (T-2d.4), which is a compound of formula (I) wherein A1 , A2, A3, A4, R7 and R8 have the specific meanings given in the Table 1 d.
Figure imgf000048_0002
Table 5d: This table discloses compounds 5d.001 to 5d.030 of the formula (T-2d.5), which is a compound of formula (I) wherein A1 , A2, A3, A4, R5, R7 and R8 have the specific meanings given in the Table 1 d.
Figure imgf000048_0003
Table 6d: This table discloses compounds 6d.001 to 6d.030 of the formula (T-2d.6), which is a compound of formula (I) wherein A1 , A2, A3, A4, R7 and R8 have the specific meanings given in the Table 1 d.
Figure imgf000048_0004
(T-2d.6) Table 7d: This table discloses compounds 7d.001 to 7d.030 of the formula (T-2d.7), which is a compound of formula (I) wherein A1 , A2, A3, A4, R7 and R8 have the specific meanings given in the Table 1 d.
Figure imgf000049_0001
Table 8d: This table discloses compounds 8d.001 to 8d.030 of the formula (T-2d.8), which is a compound of formula (I) wherein A1 , A2, A3, A4, R7 and R8 have the specific meanings given in the Table 1 d.
Figure imgf000049_0002
Table 9d: This table discloses compounds 9d.001 to 9d.030 of the formula (T-2d.9), which is a compound of formula (I) wherein A1 , A2, A3, A4, R7 and R8 have the specific meanings given in the Table 1 d.
Figure imgf000049_0003
Table 10d: This table discloses compounds 10d.001 to 10d.030 of the formula (T-2d.10), which is a compound of formula (I) wherein A1 , A2, A3, A4, R7 and R8 have the specific meanings given in the Table 1 d.
Figure imgf000050_0001
Table 1 1 d: This table discloses compounds 1 1d.001 to 1 1 d.030 of the formula (T-2d.1 1 ), which is a compound of formula (I) wherein A1 , A2, A3, A4, R7 and R8 have the specific meanings given in the Table 1 d.
Figure imgf000050_0002
Table 12d: This table discloses compounds 12d.001 to 12d.030 of the formula (T-2d.12), which is a compound of formula (I) wherein A1 , A2, A3, A4, R7 and R8 have the specific meanings given in the Table 1 d.
Figure imgf000050_0003
Table 13d: This table discloses compounds 13d.001 to 13d.030 of the formula (T-2d.13), which is a compound of formula (I) wherein A1 , A2, A3, A4, R7 and R8 have the specific meanings given in the Table 1 d.
Figure imgf000050_0004
(T-2d.13) EXAMPLES
The Examples which follow serve to illustrate the invention. The compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.
Compounds of Formula (I) 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 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.
The description of the LC/MS apparatus and the method C is:
SQ Detector 2 from Waters
lonisation method: Electrospray
ACQUITY H Class UPLC, Mass Spectrometer from Waters
Polarity: positive and Negative Polarity Switch
Scan Type MS1 Scan
Capillary (kV) 3.00, Cone (V) 40.00, Desolvation Temperature (°C) 500, Cone Gas Flow (L/Hr) 50, Desolvation Gas Flow (L/Hr) 1000
Mass range: 0 to 2000 Da
DAD Wavelength range (nm): 200 to 350
Method Waters ACQUITY UPLC with the following HPLC gradient conditions
(Solvent A: Water +,0.1 % formic acid and Solvent B: Acetonitrile)
Time (minutes) A (%) B (%) Flow rate (ml/min)
0 70 30 0.5
0.05 70 30 0.5
0.8 5 95 0.5
1.8 5 95 0.5
2.45 70 30 0.5
2.50 70 30 0.5
Type of column: Waters ACQUITY UPLC BEH C18; Column length: 50 mm; Internal diameter of column: 2.1 mm; Particle Size: 1 .7 micron; Temperature: 35°C.
Where necessary, enantiomerically pure final compounds may be obtained from racemic materials as appropriate via standard physical separation techniques, such as reverse phase chiral chromatography, or through stereoselective synthetic techniques, eg, by using chiral starting materials.
Formulation Examples
Wettable powders a) b) c)
active ingredient [compound of formula (I)] 25 % 50 % 75 %
sodium lignosulfonate 5 % 5 %
sodium lauryl sulfate 3 % - 5 %
sodium diisobutylnaphthalenesulfonate - 6 % 10 %
phenol polyethylene glycol ether - 2 %
(7-8 mol of ethylene oxide)
highly dispersed silicic acid 5 % 10 % 10 %
Kaolin 62 % 27 %
The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
Powders for dry seed treatment a) b) c)
active ingredient [compound of formula (I)] 25 % 50 % 75 %
light mineral oil 5 % 5 % 5 %
highly dispersed silicic acid 5 % 5 %
Kaolin 65 % 40 %
Talcum - 20%
The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
Emulsifiable concentrate
active ingredient [compound of formula (I)] 10 %
octylphenol polyethylene glycol ether 3 %
(4-5 mol of ethylene oxide)
calcium dodecylbenzenesulfonate 3 %
castor oil polyglycol ether (35 mol of ethylene oxide) 4 %
Cyclohexanone 30 %
xylene mixture 50 %
Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water. Dusts a) b) c)
Active ingredient [compound of formula (I)] 5 % 6 % 4 %
Talcum 95 %
Kaolin 94 %
mineral filler 96 %
Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
Extruder granules
Active ingredient [compound of formula (I)] 15 %
sodium lignosulfonate 2 %
Carboxymethylcellulose 1 %
Kaolin 82 %
The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.
Coated granules
Active ingredient [compound of formula (I)] 8 %
polyethylene glycol (mol. wt. 200) 3 %
Kaolin 89 % The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
Suspension concentrate
active ingredient [compound of formula (I)] 40 %
propylene glycol 10 %
nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
Sodium lignosulfonate 10 %
Carboxymethylcellulose 1 %
silicone oil (in the form of a 75 % emulsion in water) 1 %
Water 32 %
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion. Flowable concentrate for seed treatment active ingredient [compound of formula (I)] 40 %
propylene glycol 5 %
copolymer butanol PO/EO 2 %
tristyrenephenole with 10-20 moles EO 2 %
1 ,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 %
monoazo-pigment calcium salt 5 %
Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
Water 45.3 %
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
Slow-Release Capsule Suspension
28 parts of a combination of the compound of formula I are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8: 1 ). This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1 ,6- diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns.
The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
List of Abbreviations:
AIBN = azobisisobutyronitrile
DMF = dimethylformamide
DIPEA = N,N-di-isopropylethylamine
EtOAc = ethyl acetate
KHMDS = potassium bis(trimethylsilyl)amide
HCI = hydrochloric acid
mp = melting point
°C = degrees Celsius
MeOH = methyl alcohol
NaOH = sodium hydroxide NBS = N-bromosuccinimide
min = minutes
RT = room temperature
TFAA = trifluoroacetic acid anhydride
THF = tetrahydrofuran
= Retention time
LC/MS = Liquid Chromatography Mass Spectrometry (description of the apparatus and the methods used for LC/MS analysis are given above) Preparation Examples
Example 1 : This example illustrates the preparation 2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]isoxazolidin-3-one (Compound A-5 of Table A)
Figure imgf000056_0001
Step 1 : Preparation of N'-hvdroxy-4-methyl-benzamidine
Figure imgf000056_0002
To a stirred suspension of 4-methylbenzonitrile (35 g, 0.29 mol) in ethanol (220 mL) and water (440 mL) at RT was added hydroxylamine hydrochloride (41.1 g, 0.58 mol), potassium carbonate (65.4 g, 0.47 mol) and 8-hydroxyquinoline (0.22 g, 1.5 mmol). The reaction mixture was heated at 80°C for 4 hours. The mixture was cooled to RT and diluted with 2N HCI until pH 8. Ethanol was evaporated under reduced pressure. The mixture was filtered, washed with water and dried under vacuum to afford the title compound. LC/MS (Method A) retention time = 0.23 minutes, 151.0 (M+H). Step 2: Preparation of 3-(p-tolyl)-5-(trifluoromethyl)-1 ,2,4-oxadiazole
Figure imgf000056_0003
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 then diluted with water. The organic layer was separated, washed successively with sodium bicarbonate solution, ammonium chloride solution and water, dried over sodium sulfate, filtered and evaporated to dryness. The crude product was purified by flash chromatography over silica gel (750 g pre-packed column) with heptane/EtOAc 99:1 to 90: 10 to afford the title compound as a clear oil, which solidified upon storage. LC/MS (Method A) retention time = 1.15 minutes, mass not detected.
Ή NMR (400 MHz, CDCIs) 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-(trifluoromethvn-1 ,2,4-oxadiazole
Figure imgf000057_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 stirred at 65°C for 18 hours. The mixture was cooled to RT and diluted with dichloromethane and water. Layers were separated. The organic layer was washed with a sodium bicarbonate solution, dried over sodium sulfate, filtered and evaporated to dryness. The crude residue was purified by flash chromatography over silica gel (750 g pre-packed column) with cyclohexane/EtOAc 100:0 to 95:5 to afford the title compound as a white solid mp: 58-63°C.
Ή 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 a white solid mp: 61-66°C. Ή 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 imgf000057_0002
To a stirred 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 were added and acetonitrile was evaporated under reduced pressure. The white slurry was extracted three times 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 (40 g pre-packed column) with cyclohexane/EtOAc 99:1 to 9:1 to afford 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole.
Ή NMR (400 MHz, CDCIs) δ ppm: 8.1 1 (d, 2H), 7.55 (d, 2H), 4.53 (s,2H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.32 (s).
Step 4: Preparation of 2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyllisoxazolidin-3-one
Figure imgf000058_0001
A solution of 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (150 mg, 0.46 mmol), isoxazolidin-3-one (1 .5 equiv., 61 mg, 0.7 mmol), and potassium carbonate (2 equiv., 130 mg, 0.93 mmol) in acetonitrile (4.7 mL) was heated in a microwave oven for 30 minutes at 120°C. Solids were removed by filtration and washed with ethyl acetate and the mother liquors evaporated to give a crude residue which was purified by flash chromatography over silica gel (cyclohexane:EtOAc eluent gradient 1 :0 to 1 :1 ) to afford the title compound as a yellow solid. LC/MS (Method A) retention time = 0.96 minutes, 314 (M+H). mp: 54-58°C
Ή NMR (400 MHz, CDCI3) δ ppm: 8.22 (d, 2H), 7.49 (d, 2H), 4.75 (s, 2H), 4.30 (t, 2H), 2.80 (t, 3H)
Example 2: This example illustrates the preparation of 4,4-dimethyl-1-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]piperidine-2,6-dione (Compound A-1 1 of Table A)
Figure imgf000058_0002
To a stirred solution of n-BuLi in hexanes (1.6 M, 0.285 mL, 0.456 mmol) and THF (1 .1 mL) at -78 °C was added a solution of 4,4-dimethylpiperidine-2,6-dione ( 0.055 g, 0.39 mmol) in THF (0.3 mL). The reaction mixture was stirred for 30 minutes at -78 °C and then 3-[4-(bromomethyl)phenyl]-5- (trifluoromethyl)-1 ,2,4-oxadiazole (0.100 g, 0.326 mmol) was added. The reaction mixture was then warmed to 0°C and stirred at this temperature for 1 h. The reaction mixture was further warmed to RT and stirred overnight before being quenched at 0°C with a saturated NhUCI solution. The mixture was extracted with ethyl acetate and the combined organic layers washed with brine, dried over Na2S04, filtered and concentrated. The residue obtained was purified by flash chromatography over silica gel using cyclohexane/AcOEt as eluent to give 4,4-dimethyl-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]piperidine-2,6-dione as a colorless oil. LC/MS (Method A) retention time = 1.14 minutes, 368 (M+H).
Ή NMR (400 MHz, CDCIs) δ ppm 0.96 - 1.04 (s, 6 H) 2.48 (s, 4 H) 4.95 (s, 2 H) 7.45 (d, 2 H) 7.97 (d, 2 H)
Example 3: This example illustrates the preparation of 4-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]morpholin-3-one Compound A-3 of Table A)
Figure imgf000059_0001
A solution of 4-(bromomethyl)benzonitrile (2.0 g, 10.2 mmol), morpholin-3-one (2.5 equiv., 2.1 1 g, 20.9 mmol), and potassium carbonate (2 equiv., 2.82 g, 20.4 mmol) in acetonitrile (4.7 mL) was heated at 85°C for 19 hours. After cooling to 25°C, the solvent was removed under reduced pressure. The residue obtained was dissolved in ethyl acetate and washed with water. The organic layer was then dried over sodium sulfate, and concentrated under reduced pressure. The crude yellow residue obtained was purified by flash chromatography over silica gel (cyclohexane:EtOAc eluent gradient 9: 1 to 0: 1 ) to give 1.13 g (51 % yield) of the title compound as a yellow oil. LC/MS (Method A) retention time = 0.58 minutes, 217 (M+H).
Ή NMR (400 MHz, CDCI3) δ ppm: 7.65 (d, 2H), 7.38(d, 2H), 4.68 (s, 2H), 4.25 (t, 2H), 3.85 (t, 2H), 3.30 (t, 2H).
Step 2: N-hvdroxy-4-[(3-oxomorpholin-4-yl)methvHbenzamidine
Figure imgf000060_0001
In a flask under argon, to hydroxylamine hydrochloride (3.0 equiv., 1.09 g 15.7 mmol) and ethanol (10.5 mL) was added triethylamine (3.0 equiv., 2.19 mL, 15.7 mol) at 25°C. The resultant suspension was allowed to stir for 30 minutes after which 4-[(3-oxomorpholin-4-yl)methyl]benzonitrile (1.13 g, 5.23 mmol) was introduced and the reaction mixture heated at a temperature of 50°C for 6 hours. Ethanol was evaporated under reduced pressure and the crude reaction mixture taken up in the next step without additional purification or characterization. LC/MS (Method A) retention time = 0.23 minutes, 151 .0 (M+H).
Figure imgf000060_0002
To a stirred solution of crude N-hydroxy-4-[(3-oxomorpholin-4-yl)methyl]benzamidine (5.23 mmol) in tetrahydrofuran (10 mL) was added drop-wise trifluoroacetic anhydride (1.5 equiv, 1.1 mL, 7.8 mmol) at 25°C. The solvent was removed under reduced pressure, affording an orange oil which was dissolved in a minimal amount of dichloromethane and then washed with a saturated aqueous sodium bicarbonate solution. The organic phase was dried over sodium sulfate, filtrated, and solvent was removed under vacuum. The crude residue was purified by combiflash chromatography over silica gel (heptane: EtOAc eluent gradient 99: 1 to 90: 10) to afford 850 mg (50% yield) of the title compound as colorless oil. LC/MS (Method A) retention time = 0.92 minutes, 328 (M+H).
Ή NMR (400 MHz, CDCIs) δ ppm: 8.10 (d, 2H), 7.45 (d, 2H), 4.70 (s, 2H), 4.37 (s, 2H), 3.85 (t, 2H), 3.30 (t, 2H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.33 (s).
Example 4: This example illustrates the preparation of 1-[[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2- pyridyl]methyl]piperidin-2-one (Compound A-12 of Table A)
Figure imgf000061_0001
Step 1 : N'-hvdroxy-6-methyl-pyridine-3-carboxamidine
Figure imgf000061_0002
To a stirred suspension of 5-cyano-2-picoline (3.0 g, 25.4 mmol) in ethanol (86 imL) was added at RT hydroxylamine hydrochloride (5.2 g, 76.0 mmol) and triethylamine (10.6 g, 76.0 mmol). The reaction mixture was heated at 80°C for 2 hours. The mixture was cooled to RT and the ethanol evaporated under reduced pressure. The mixture was filtered, washed with water and dried under vacuum to afford 3.8 g of the title compound used without further purification.
Step 2: Preparation of 3-(6-methyl-3-pyridyl)-5-(trifluoromethyl)-1 ,2,4-oxadiazole
Figure imgf000061_0003
To a stirred solution of N'-hydroxy-6-methyl-pyridine-3-carboxamidine (3.83 g, 25.3 mmol) in tetrahydrofuran (84 mL) was added TFAA (5.3 mL, 38 mmol) at 0°C. The reaction mixture was stirred at 15°C for two hours and diluted with water. The organic layer was separated, washed successively with sodium bicarbonate solution, ammonium chloride solution and water, dried over sodium sulfate, filtered and evaporated to dryness to afford 5.8 g of the title compound as clear oil used without further purification. LC/MS (Method A) retention time = 0.97 minutes, 230 (M+H).
Ή NMR (400 MHz, CDCIs) δ ppm: 9.23 (d, 2H), 8.26 (d, 2H), 7.35 (d, 2H), 2.66 (s, 3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.3 (s).
Step 3a: Preparation of 3-[6-(bromomethyl)-3-pyridyll-5-(trifluoromethyl)-1 ,2,4-oxadiazole
Figure imgf000061_0004
A stirred mixture of 3-(6-methyl-3-pyridyl)-5-(trifluoromethyl)-1 ,2,4-oxadiazole (2.2 g, 7.1 mmol) and NBS (3.5 g, 19.0 mmol) in tetrachloromethane (38 mL) under argon was heated to 70°C. AIBN (4.03 g, 24 mmol) was added portion-wise and the reaction mixture stirred at 65°C for 18 hours. The mixture was cooled to 25°C and diluted with dichloromethane and water. The organic layer was washed with a sodium bicarbonate solution, dried over sodium sulfate, filtered and evaporated to dryness. The crude residue was subjected to flash chromatography over silica gel with cyclohexane/EtOAc 100:0 to 80:20 to afford 2.2 g of the title compound as a white solid.
LC/MS (Method A) retention time = 1.01 minutes, no mass detected
Ή NMR (400 MHz, CDCIs) δ ppm: 9.25 (s, 1 H), 8.40 (dd, 1 H), 7.63 (d, 1 H), 4.6 (s, 2H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.2 (s).
3-[6-(dibromomethyl)-3-pyridyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (see below) was isolated as by-product as a beige oil in 44% yield (3.2g, containing ca. 10% of 3-[6-(bromomethyl)-3-pyridyl]-5- (trifluoromethyl)-l ,2,4-oxadiazole .
Figure imgf000062_0001
LC/MS (Method A) retention time = 1.10 minutes, 388 (M+H).
Ή NMR (400 MHz, CDCI3) δ ppm: 9.25 (s, 1 H), 8.50 (dd, 1 H), 7.98 (d, 1 H), 6.71 (s, 1 H). 9F NMR (400 MHz, CDCI3) δ ppm: -65.2 (s).
Step 3b: Preparation of 3-[6-(bromomethyl)-3-pyridyll-5-(trifluoromethyl)-1 ,2,4-oxadiazole
Figure imgf000062_0002
To a stirred 1 :9 ratio mixture of 3-[6-(bromomethyl)-3-pyridyl]-5-(trifluoromethyl)-1 ,2,4- oxadiazole and 3-[6-(dibromomethyl)-3-pyridyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (3.24 g, 8.4 mmol) in acetonitrile (35 mL), water (0.7 mL) and DIPEA (2.2 ml, 12.6 mmol) was added diethylphosphite (1.65 ml, 12.6 mmol) at 5°C. The mixture was stirred at 5-10°C for two hours, water and 1 M HCI were added, and acetonitrile evaporated under reduced pressure. The white slurry was extracted with dichloromethane and the combined organic layers dried over sodium sulfate, and filtered. The solvent was removed under reduced pressure and the resultant crude mixture subjected to combiflash chromatography over silica gel with cyclohexane/EtOAc 99:1 to 1 : 1 to afford 2.3 g of 3-[6- (bromomethyl)-3-pyridyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole.
LC/MS (Method A) retention time = 1.01 minutes, no mass detected „„
62
Ή NMR (400 MHz, CDCIs) δ ppm: 9.25 (s, 1 H), 8.40 (dd, 1 H), 7.63 (d, 1 H), 4.6 (s, 2H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.2 (s).
Step 4: Preparation of 1-[[5-[5-(trifluoromethvn-1 ,2,4-oxadiazol-3-yll-2-pyridyllmethyllpiperidin-2-one
Figure imgf000063_0001
To a stirred solution of n-BuLi (1.6 M in hexanes) (0.57 ml_, 0.91 mmol) in THF (2.16 ml_, 0.65 mmol) at -78 °C was added a solution of piperidin-2-one in THF (3.3 ml_). After 20 min at -78 °C, 3-[6- (bromomethyl)-3-pyridyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (0.2 g, 0.65 mmol) was added and the reaction mixture stirred at -78°C for 3.5 hours after which time the reaction mixture was left in the fridge without stirring over the weekend. LCMS showed completion. The reaction mixture was quenched at 0°C with a sat. NH4CI solution and the solution extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, concentrated and purified by combiflash chromatography over silica gel using a cyclohexane/AcOEt as eluent to afford 0.21 g of the title compound as yellow oil.
LC/MS (Method A) retention time = 0.89 minutes, 327 (M+H)
Ή NMR (400 MHz, CDCI3) δ ppm: 9.25 (d, 1 H), 8.35 (d, 1 H), 7.45 (d, 1 H), 4.78 (s, 2H), 3.40
(m, 2H), 2.48 (m, 2H), 1.83 (m, 4H)
9F NMR (400 MHz, CDCI3) δ ppm: -65.25 (s).
Example 5: This example illustrates the preparation of 2-[[2-chloro-4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]-1 ,2-thiazolidine 1 , 1-dioxide (Compound B-2 of Table B )
Figure imgf000063_0002
To a stirred solution of KHMDS in THF (1 M, 0.410 ml_, 0.410 mmol) and THF (1 mL) at 0 °C was added a solution of 1 , 1-dioxo-isothiazolidine (0.044 g, 0.35 mmol) in THF (0.5ml_). The reaction mixture was stirred for 30 minutes at 0 °C and then 3-[4-(bromomethyl)-3-chloro-phenyl]-5- (trifluoromethyl)-1 ,2,4-oxadiazole (0.100 g, 0.293 mmol), prepared according to procedures described in example 1 using 3-chloro-4-methyl-benzonitrile as starting material, was added. The reaction mixture was stirred at 0°C for 2 h. The reaction mixture was then quenched with water and warmed to RT. The mixture was extracted with ethyl acetate and the combined organic layers washed with brine, dried over MgSC , filtered and concentrated under reduce pressure. LC/MS (Method A) retention time = 1.07 minutes, 398 (M+OH)". The mass observed only in the negative ionization and corresponded to that of a hydrated species.
Example 6: This example illustrates the preparation of 2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]-1 ,2-thiazolidine 1 , 1 -dioxide (Compound D-1 of Table D)
Figure imgf000064_0001
A sealed tube was charged with 4-iodobenzonitrile (0.50 g, 2.2 mmol), 1 ,2-thiazolidine 1 , 1- dioxide (1.2 equiv.; 0.32 g, 2.6 mmol), dimethylethylenediamine (0.1 equiv., 0.23 mL, 0.22 mmol), cesium fluoride (2.5 equiv., 0.83 g, 5.47 mmol), copper iodide (0.05 equiv., 0.02 g, 0.10 mmol), tetrahydrofuran (4.7 mL) and the reaction contents were stirred at room temperature for 24 hours. The reaction contents were diluted with ethyl acetate and a saturated aqueous ammonium chloride solution. The layers were separated and the organic fraction was washed with water, dried over sodium sulfate, and concentrated under reduced pressure. The corresponding crude yellow oil (449 mg) was taken up in the next step without additional purification or characterization.
Ή NMR (400 MHz, CDCIs) δ ppm: 7.85 (d, 2H), 7.30 (d, 2H), 3.82 (t, 2H), 3.28 (t, 2H), 3.30 (m, 2H).
Step 2: 4-(1 ,1-dioxo-1 ,2-thiazolidi
Figure imgf000064_0002
In a flask under argon, to hydroxylamine hydrochloride (3.0 equiv., 0.42 g 6.0 mmol) and ethanol (5 mL) was added triethylamine (3.0 equiv., 0.85 mL, 6.0 mmol) at 25°C. The resultant suspension was allowed to stir for 30 minutes after which 4-(1 , 1-dioxo-1 ,2-thiazolidin-2-yl)benzonitrile (0.45 g, 2.0 mmol) was introduced and the reaction mixture heated at a temperature of 50°C for 6 „
64
hours. Ethanol was evaporated under reduced pressure and the crude reaction mixture taken up in the next step without additional purification or characterization.
Step 3: 2-[4-[5-(trifluoromethvn ,2-thiazolidine 1 , 1-dioxide
Figure imgf000065_0001
To a stirred solution of crude 4-(1 , 1-dioxo-1 ,2-thiazolidin-2-yl)-N-hydroxy-benzamidine (0.2 g, 2.0 mmol) in tetrahydrofuran (4 mL) was added dropwise trifluoroacetic anhydride (1.5 equiv, 0.43 mL, 3.0 mmol) at 25°C. The solvent was removed under reduced pressure, affording an orange oil which was dissolved in a minimal amount of dichloromethane and then washed with a saturated aqueous sodium bicarbonate solution. The organic phase was dried over sodium sulfate, filtrated, and solvent was removed under vacuum. The crude residue was purified by combiflash chromatography over silica gel (cyclohexane:EtOAc eluent gradient 9:1 to 1 :9) to afford 0.21 g (50% yield) of the title compound as a beige solid (melting point range = 154 - 158°C). LC/MS (Method A) retention time = 0.97 minutes, 350 (M+OH)". The mass observed only in the negative ionization and corresponded to that of a hydrated species.
Ή NMR (400 MHz, CDCIs) δ ppm: 8.1 1 (d, 2H), 7.35 (d, 2H), 3.86 (t, 2H), 3.44 (t, 2H), 2.60 (m, 2H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.36 (s).
Example 7: This example illustrates the preparation of 2 2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]isoxazolidin-3-one (Compound C-2 of Table C)
Figure imgf000065_0002
Step 1 : 4-(3-oxoisoxazolidin-2-yl)benzonitrile
Figure imgf000065_0003
A sealed tube was charged with 4-iodobenzonitrile (1.0 g, 4.4 mmol), isoxazolidin-3-one (1 .2 equiv.; 0.46 g, 5.2 mmol), dimethylethylenediamine (0.1 equiv., 0.47 mL, 0.44 mmol), cesium fluoride (2.5 equiv., 1.66 g, 10.9 mmol), copper iodide (0.05 equiv., 0.04 g, 0.20 mmol), tetrahydrofuran (8 imL) and the reaction contents were stirred at room temperature for 24 hours. The reaction contents were diluted with ethyl acetate and a saturated aqueous ammonium chloride solution. The layers were separated and the organic fraction was washed with water, dried over sodium sulfate, and concentrated under reduced pressure. The crude residue was purified by combiflash chromatography over silica gel (cyclohexane:EtOAc eluent gradient 9:1 to 1 :9) to afford 0.82 g (50% yield) of the title compound as an amorphous brown solid.
LC/MS (Method A) retention time = 0.72 minutes, 188 (M+H)+.
Ή NMR (400 MHz, CDCIs) δ ppm: 7.83 (d, 2H), 7.65 (d, 2H), 4.59 (t, 2H), 3.07 (t, 2H), 3.30
(m, 2H).
Figure imgf000066_0001
In a flask under argon, to hydroxylamine hydrochloride (3.0 equiv., 0.48 g, 7.0 mmol) and ethanol (6 mL) was added triethylamine (3.0 equiv., 0.97 mL, 7.0 mmol) at 25°C. The resultant suspension was allowed to stir for 30 minutes after which 4-(3-oxoisoxazolidin-2-yl)benzonitrile (0.44 g, 2.3 mmol) was introduced and the reaction mixture heated at a temperature of 50°C for 6 hours. Ethanol was evaporated under reduced pressure and the crude reaction mixture taken up in the next step without additional purification or characterization.
Step 3: 2 2-[4-[5-(trifluoromethvn-1 ,2,4-oxadiazol-3-yllphenyllisoxazolidin-3-one
Figure imgf000066_0002
To a stirred solution of crude N-hydroxy-4-(3-oxoisoxazolidin-2-yl)benzamidine (0.51 g, 2.3 mmol) in tetrahydrofuran (10 mL) was added dropwise trifluoroacetic anhydride (1.5 equiv, 0.49 mL, 3.4 mmol) at 25°C. The solvent was removed under reduced pressure, affording an orange oil which was dissolved in a minimal amount of dichloromethane and then washed with a saturated aqueous sodium bicarbonate solution. The organic phase was dried over sodium sulfate, filtrated, and solvent was removed under vacuum. The crude residue was purified by combiflash chromatography over silica gel (cyclohexane:EtOAc eluent gradient 9:1 to 1 :9) to afford 0.13 g (19% yield) of the title compound as a white solid (melting point range = 74 - 77°C).
LC/MS (Method A) retention time = 1.03 minutes, 300 (M+H) Ή NMR (400 MHz, CDCIs) δ ppm: 8.13 (d, 2H), 7.87 (d, 2H), 4.59 (t, 2H), 3.07 (t, 2H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.37 (s).
Example 8: This example illustrates the preparation of tert-butyl 3-oxo-4-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]meth l]piperazine-1-carboxylate (Compound A-30 of Table A)
Figure imgf000067_0001
To a stirred solution of KHMDS in THF (0.456 ml_, 0.456 mmol) in THF (1.1 mL) at 0°C was added a solution of 1-Boc-3-oxopiperazine (0.091 g, 0.456 mmol) in THF (0.33 ml). After 30 min at 0°C, 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (0.100 g, 0.326 mmol) was added and the reaction mixture was stirred for 1 h at 0°C. The reaction mixture was left at 4 °C overnight without stirring. The reaction mixture was quenched at 0°C with a 1 M HCI solution and the mixture was extracted with EtOAc. The combined organic layers were washed with brine, dried over Na2S04, filtered, concentrated and purified by Isco combiflash Rf using cyclohexane/AcOEt as eluent to give tert-butyl 3-oxo-4-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]piperazine-1-carboxylate as a white solid.
Ή NMR (400 MHz, CDCI3) δ ppm: 1.40 (s, 9H) 3.23 (t, J=5.1 Hz, 2H) 3.56 (t, J=5.3 Hz, 2H) 4.12 (s, 2H) 4.63 (s, 2H) 7.35 (d, J=8.4 Hz, 2H) 8.03 (d, J=8.1 Hz, 2H)
LC/MS (Method A) retention time = 1.09 min, 443 [M+OH]"
mp: 96-99°C
Example 9: This example illustrates the preparation of N,N-dimethyl-3-oxo-4-[[4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]phenyl]meth l]piperazine-1-carboxamide (Compound A-34 of Table A)
Figure imgf000067_0002
Step 1 : 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyllpiperazin-2-one hydrochloride (Compound A-36 of Table A)
Figure imgf000068_0001
solution of tert-butyl 3-oxo-4-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]- phenyl]methyl]piperazine-1-carboxylate (0.375 g, 0.879 mmol) (from Example 8) in THF (2.9 mL) was added HCI in dioxane (2.20 mL, 8.79 mmol). The reaction mixture was stirred for 50 min at RT and then heated to 60 °C for an additional 2 h. All the volatiles were evaporated to give 1-[[4-[5- (trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]piperazin-2-one hydrochloride as a white solid. The product was used in the next step without further purification.
Ή NMR (400 MHz, DMSO-d6) δ ppm: 3.39 (s, 2H) 3.41 - 3.49 (m, 2H) 3.49 - 3.57 (m, 2H) 4.71 (s, 2H) 7.58 (d, J=8.4 Hz, 2H) 8.07 (d, J=8.4 Hz, 2H) 9.71 (br. s., 2H)
LC/MS (Method A) retention time = 0.72 min; 327 [M+H]+
Step 2: N,N-dimethyl-3-oxo-4-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyllpiperazine-1- carboxamide
To a solution of 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]piperazin-2-one hydrochloride (0.050 g, 0.14 mmol) in dichloromethane (0.5 mL) was added N,N-dimethylcarbamoyl chloride (0.025 mL, 0.28 mmol) followed by triethylamine (0.058 mL, 0.41 mmol). The reaction mixture was stirred for 2.5 h at RT, after which a saturated aq. NaHCCh solution was added and the aqueous phase was extracted with dichloromethane. The combined organic layers were dried over Na2S04, filtered, concentrated and purified by Isco combiflash Rf using CH2Cl2 MeOH as eluent to give N,N- dimethyl-3-oxo-4-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]piperazine-1-carboxamide as a white solid.
Ή NMR (400 MHz, CDCIs) δ ppm: 2.79 (s, 6H) 3.27 - 3.33 (m, 2H) 3.35 - 3.46 (m, 2H) 3.96 (s, 2H) 4.61 (s, 2H) 7.35 (d, J=8.1 Hz, 2H) 8.02 (d, J=8.1 Hz, 2H)
LC/MS (Method A) retention time = 0.91 min; 398 [M+H] l +
mp: 1 11-114°C
Example 10: This example illustrates the preparation of N,N-dimethyl-3-oxo-4-[[4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]phenyl]methyl]piperazine-1-sulfonamide (Compound A-42 of Table A)
Figure imgf000069_0001
To a solution of 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]piperazin-2-one hydrochloride (0.050 g, 0.14 mmol) in dichloromethane (0.5 mL) was added N,N-dimethylsulfamoyl chloride (0.030 mL, 0.28 mmol) followed by triethylamine (0.058 mL, 0.41 mmol). The reaction mixture was stirred for 80 min at RT, after which a saturated aq. NaHCCh solution was added and the aqueous phase was extracted with dichloromethane. The combined organic layers were dried over Na2S04, filtered, concentrated and purified by Isco combiflash Rf using ChbCk/MeOH as eluent to give N,N- dimethyl-3-oxo-4-[[4-[5-(trifluoromethyl)-1 , 2, 4-oxadiazol-3-yl]phenyl]methyl]piperazine-1 -sulfonamide as a white solid.
Ή NMR (400 MHz, CDCIs) δ ppm: 2.80 (s, 6H) 3.28 - 3.34 (m, 2H) 3.39 - 3.46 (m, 2H) 3.88 (s, 2H) 4.64 (s, 2H) 7.35 (d, J=8.4 Hz, 2H) 8.03 (d, J=8.4 Hz, 2H)
LC/MS (Method A) retention time = 1.00 min; 434 [M+H]+
Example 1 1 : This example illustrates the preparation of 1-methoxy-3-[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]imidazolidin-2-one Compound C-3 of Table C)
Figure imgf000069_0002
Step 1 : 1-methoxy-3-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllurea
Figure imgf000069_0003
To a solution of 4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]aniline (2.00 g, 8.73 mmol) in THF (29 mL) was added carbonyldiimidazole (2.12 g, 13.1 mmol) followed by methoxylamine hydrochloride (0.948 g, 1 1.3 mmol) and DIPEA (1.94 mL, 1 1.3 mmol). The reaction mixture was stirred for 5 hours at 55°C. All the solvents were then evaporated and the residue was purified by Isco combiflash Rf using _
69
cyclohexane/EtOAc as eluent to give 1-methoxy-3-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]urea as a white solid.
Ή NMR (400 MHz, CDCIs) δ ppm: 7.61 (d, J=8.8 Hz, 2H) 7.66 (br. s., 1 H) 8.02 (d, J=8.4 Hz, 2H).
LC/MS (Method A) retention time = 0.93 min; 303 [M+H]+ Step 2: 1-methoxy-3-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllimidazolidin-2-one To a stirred solution of 1-methoxy-3-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]urea
(0.100 g, 0.331 mmol) in DMF (1.1 mL) at room temperature was added NaH (0.015 g, 0.364 mmol). The reaction mixture was stirred for 30 min and then 1 ,2-dibromoethane (0.030 mL, 0.35 mmol) was added. After an additional 30 min, a second portion of NaH (0.015 g, 0.364 mmol) was added. The reaction mixture was stirred for 1 h at RT and then poured in water and extracted with AcOEt. The combined organic layers were washed with brine, dried over Na2S04, filtered, concentrated and purified by Isco combiflash Rf using cyclohexane/AcOEt. The solid obtained was further purified by recrystallization from CH2CI2 and MeOH to give 1-methoxy-3-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]imidazolidin-2-one as white crystals.
Ή NMR (400 MHz, CDCI3) δ ppm: 3.54 - 3.65 (m, 2H) 3.70 - 3.79 (m, 2H) 3.82 (s, 3H) 7.69 (d, J=8.8 Hz, 2H) 8.05 (d, J=8.0 Hz, 2H)
LC/MS (Method A) retention time = 1.02 min; 329 [M+H]+
mp: 185-190°C
Example 12: This example illustrates the preparation 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]azepan-2-one (Compound A-70 of Table A)
Figure imgf000070_0001
To a solution of nBuLi (1.6M in hexanes 0.712 mL, 1.14 mmol) in THF (3 mL) at -78 °C was introduced a solution of azepan-2-one (137 g, 1 .22 mmol) in THF (3 mL). After 20 min at -78 °C, 3-[4- (bromomethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (0.25 g, 0.81 mmol) was added and the reaction mixture was stirred for 3 hours while warming from -78°C to 0°C using an ice bath. The reaction mixture was then left in the refrigerator (5°C) overnight without stirring. Then, the reaction mixture was quenched at 0°C with a saturated ammonium chloride solution and extracted with ethyl acetate. The total combined organic layer was washed with brine, dried over Na2S04, filtered, and concentrated under reduced pressure. The crude residue was purified by combiflash column chroatography (cyclohexane/ethyl acetate eluent gradient 1 :0 to 1 : 1 ) to give 1-[[4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]phenyl]methyl]azepan-2-one as a colourless oil. (75 mg, 27% yield).
Ή NMR (400 MHz, CDCIs) δ ppm: 8.08 (d, 2H), 7.40 (d, 2H), 4.66 (s, 2H), 3.33 (m, 2H), 2.64 (m, 2H), 1.72 (m, 4H), 1.30 (m, 2H).
LC/MS (Method A) retention time = 1.06 minutes, 340 (M+H).
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 A: Meltinq point (mp) and/or LC/MS data for compounds of Formula (I):
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
A-55 4-acetyl-1-[[4-[5- 111 - (trifluoromethyl)- 114 1,2,4-oxadiazol-3- yl]phenyl]methyl]pi
perazine-2,6-dione
A-56 N,N-dimethyl-3,5- 138- dioxo-4-[[4-[5- 141 (trifluoromethyl)- 1,2,4-oxadiazol-3- yl]phenyl]methyl]pi
perazine-1-
Figure imgf000081_0002
carboxamide
Figure imgf000081_0003
Entry Compound Structure tR [M+H]+ Method mp Name (min) (measured) > (°C)
A-58 N-methyl-3,5- 148 - dioxo-4-[[4-[5- 153 (trifluoromethyl)- 1 ,2,4-oxadiazol-3- yl]phenyl]methyl]pi
perazine-1-
Figure imgf000082_0001
carboxamide
1.00 419 A
Figure imgf000082_0002
A-60 N,N-dimethyl-3,5- 1.06 448 A
dioxo-4-[[4-[5- (trifluoromethyl)- 1 ,2,4-oxadiazol-3- yl]phenyl]methyl]pi
perazine-1-
Figure imgf000082_0003
sulfonamide
A-61 1-[[4-[5- 341 (M-CI)
(trifluoromethyl)-
1 ,2,4-oxadiazol-3- yl]phenyl]methyl]pi
perazin-4-ium-2,6- dione;chloride
A-62 tert-butyl 3,5- 94 - dioxo-4-[[4-[5- 102 (trifluoromethyl)- 1 ,2,4-oxadiazol-3- yl]phenyl]methyl]pi
perazine-1-
Figure imgf000082_0004
carboxylate
Figure imgf000083_0001
Figure imgf000084_0001
Table B: Melting point (mp) and/or LC/MS data for compounds of Formula (I):
Figure imgf000084_0002
Entry Compound Name Structure tR I [M+H]+ ) Method j mp
(min) j (measured) | (°C)
B-4 2-[[2-chloro-4-[5- 1 .15 410 A
(trifluorornethyl)-1 ,2,4- oxadiazol-3- yl]phenyl]methyl]-6- methyl-1 ,2,6- thiadiazinane 1 ,1-dioxide
Figure imgf000085_0001
Table C: Melting point (mp) and/or LC/MS data for compounds of Formula (I):
Figure imgf000085_0002
Table D: Melting point (mp) and/or LC/MS data for compounds of Formula (I):
Figure imgf000085_0003
BIOLOGICAL EXAMPLES:
General examples of leaf disk tests in well plates:
5
Leaf disks or leaf segments of various plant species are cut from plants grown in a greenhouse. The cut leaf disks or segments are placed in multiwell plates (24-well format) onto water agar. The leaf disks are sprayed with a test solution before (preventative) or after (curative) inoculation. Compounds to be tested are prepared as DMSO solutions (max. 10 mg/ml) which are diluted to the appropriate 10 concentration with 0.025% Tween20 just before spraying. The inoculated leaf disks or segments are incubated under defined conditions (temperature, relative humidity, light, etc.) according to the respective test system. A single evaluation of disease level is carried out 3 to 14 days after inoculation, depending on the pathosystem. Percent disease control relative to the untreated check leaf disks or segments is then calculated.
15
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
20 test compound (max. 10 mg/ml) is 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
25 antifungal activity relative to the untreated check is calculated.
Example 1 : Fungicidal activity against Glomerella lagenarium (Colletotrichum lagenarium) liquid culture / cucumber / preventative (Anthracnose)
30 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 3-4 days after application.
35 The following compounds from Tables A to D gave at least 80% control of Glomerella lagenarium at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development:
Compounds (from Table A): A-1 , A-4, A-5, A-6, A-7, A-8, A-9, A-10, A-1 1 , A-12, A-13, A-14, A- 40 15, A-16, A-17, A-18, A-19, A-20, A-21 , A-22, A-23, A-24, A-25, A-26, A-27, A-28, A-29, A-30, A-31 , A-32, A-33, A-34, A-35, A-37, A-39, A-40, A-41 , A-42, A-43, A-44, A-45, A-46, A-47, A-48, A-49, A-50, „„
86
A-51 , A-52, A-54, A-55, A-56, A-57, A-58, A-59, A-61 , A-62, A-63, A-64, A-65, A-66, A-67, A-68, A-69, and A-70.
Compounds (from Table B): B-1 , B-2, B-3, and B-4.
Compounds (from Table C): C-1 , C-2, and C-3.
Compounds (from Table D): D-1.
Example 2: 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 - 14 days after application).
The following compounds from Tables A to D gave at least 80% control of Phakopsora pachyrhizi at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development:
Compounds (from Table A): A-1 , A-2, A-3, A-4, A-5, A-6, A-7, A-8, A-9, A-10, A-1 1 , A-12, A- 13, A-14, A-15, A-16, A-17, A-18, A-19, A-20, A-21 , A-22, A-23, A-24, A-25, A-26, A-27, A-29, A-32, A- 33, A-34, A-35, A-37, A-38, A-39, A-40, A-41 , A-42, A-43, A-46, A-47, A-48, A-49, A-50, A-51 , A-54, A-55, A-56, A-57, A-58, A-59, A-60, A-65, A-66, A-67, A-68, and A-70.
Compounds (from Table B): B-1.
Compounds (from Table C): C-1 and C-2.
Compounds (from Table D): D-1.
Example 3: 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 inoculated with a spore suspension of the fungus. Plates are stored in darkness at 19 °C and 75% rh. The formulated test compound diluted in water is applied 1 day after inoculation. The leaf segments are incubated at 19 °C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and 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 segments (6 - 8 days after application).
The following compounds from Tables A to D gave at least 80% control of Puccinia recondita f. sp. tritici at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: Compounds (from Table A): A-1 , A-2, A-3, A-4, A-5, A-6, A-7, A-8, A-9, A-10, A-1 1 , A-12, A- 13, A-14, A-15, A-16, A-17, A-18, A-19, A-20, A-21 , A-22, A-23, A-24, A-25, A-26, A-27, A-28, A-29, A-30, A-31 , A-32, A-33, A-34, A-35, A-37, A-38, A-39, A-40, A-41 , A-42, A-43, A-44, A-45, A-46, A-47, 5 A-48, A-49, A-50, A-51 , A-53, A-54, A-55, A-56, A-63, A-66, A-67, A-68, and A-70.
Compounds (from Table B): B-1 , and B-3.
Compounds (from Table C): C-1 , andC-2.
Compounds (from Table D): D-1.
10 Example 4: Fungicidal activity against Puccinia recondita f. sp. tritici I wheat / leaf disc preventative (Brown rust)
Wheat leaf segments cv. Kanzler are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf segments are inoculated with a 15 spore suspension of the fungus 1 day after application. The inoculated leaf segments are incubated at 19 °C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and 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 segments (7 - 9 days after application).
20 The following compounds from Tables A to D gave at least 80% control of Puccinia recondita f. sp. tritici at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development:
Compounds (from Table A): A-1 , A-2, A-3, A-4, A-5, A-6, A-7, A-8, A-9, A-10, A-1 1 , A-12, A- 25 13, A-14, A-15, A-16, A-17, A-18, A-19, A-20, A-21 , A-22, A-23, A-24, A-25, A-26, A-27, A-28, A-29, A-30, A-31 , A-32, A-33, A-34, A-35, A-36, A-37, A-38, A-39, A-40, A-41 , A-42, A-43, A-44, A-45, A-46, A-47, A-48, A-49, A-50, A-51 , A-53, A-54, A-55, A-56, A-57, A-58, A-59, A-60, A-62, A-63, A-64, A-65, A-66, A-68, A-69, and A-70.
Compounds (from Table B): B-1 , B-2, and B-3.
30 Compounds (from Table C): C-1 and C-2.
Compounds (from Table D): D-1.
Example 5: Fungicidal activity against Uromyces viciae-fabae I field bean / leaf disc preventative (Faba-bean rust)
35
Field bean leaf discs are placed on water agar in multiwell plates (96-well format) and 10 μΙ of the formulated test compound diluted in acetone and a spreader pipetted onto the leaf disc. Two hours after application leaf discs are inoculated by spraying a spore suspension on the lower leaf surface. The leaf discs are incubated in a climate cabinet at 22°C with 18 hour day and 70% relative humidity. 40 The activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (12 days after application). „„
88
The following compounds from Tables A to D gave at least 80% control of Uromyces viciae- fabae at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: Compounds (from Table A): A-1 , A-2, and A-3.
Compounds (from Table B): B-1.
Compounds (from Table C): C-1 and C-2.
Compounds (from Table D): D-1.

Claims

Claims:
1. A compound of formula (I):
Figure imgf000090_0001
wherein n is 0 or 1 or 2;
A1 represents N or CR\ wherein R represents hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy;
A2 represents N or CR2, wherein R2 represents hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy; A3 represents N or CR3, wherein R3 represents hydrogen or halogen;
A4 represents N or CR4, wherein R4 represents hydrogen or halogen; and wherein no more than two of A1 to A4 are N;
R5 and R6 independently represent hydrogen, halogen, cyano, difluoromethyl, trifluoromethyl, or Ci-4alkyl, or together with the carbon atom to which they are bonded represent cyclopropyl;
Z represents a roup selected from Z-1 , Z-2, Z-3 or Z-4:
Figure imgf000090_0002
(Z-1 ) (Z-2) (Z-3) (Z-4) wherein:
X represents C(O) or S(0)2; and
0) B and B2 in Z-1 represent C(R7)(R8); or B\ B2 and B3 in Z-2 independently represent C(R7)(R8), O, S, NR9 or C(=0), wherein only one of B\ B2 and B3 may be a group selected from O, S, NR9 or C(=0); or
B\ B2, B3 and B4 in Z-3 independently represent C(R7)(R8), O, S, NR9 or C(=0), wherein only one of B\ B2, B3 and B4 may be a group selected from O, S or C(=0), and only one of B\ B2, B3 and B4 may be NR9; or
B in Z-2 is C(R7)(R8) and B2-B3 is a group selected from NR9C(=0), C(=0)NR9, N=N, C(R7)=C(R8), C(R8)=N or N=C(R8); or B3 in Z-2 is C(R7)(R8) and B -B2 is a group selected from NR9C(=0), C(=0)NR9, N=N, C(R7)=C(R8), C(R8)=N or N=C(R8); or
B and B2 in Z-3 are C(R7)(R8) and B3-B4 is a group selected from NR9C(=0), C(=0)NR9, N=N, C(R7)=C(R8), C(R8)=N or N=C(R8); B and B4 in Z-3 are C(R7)(R8) and B2-B3 is a group selected from NR9C(=0), C(=0)NR9, N=N, C(R7)=C(R8), C(R8)=N or N=C(R8); or B3 and B4 in Z-3 are C(R7)(R8) and B -B2 is a group selected from NR9C(=0), C(=0)NR9, N=N, C(R7)=C(R8), C(R8)=N or N=C(R8); or
B1, B2, B3, B4 and B5 in Z-4 independently represent C(R7)(R8), O, S, NR9 or C(=0), wherein only one of B\ B2, B3, B4 and B5 may be a group selected from O, S, NR9 or C(=0); or
Z represents a group selected from Z-5, wherein Z-5 represents Z-5a, Z-5b, Z-5c, Z-5d, Z-5e, Z-5f or Z-5g:
Figure imgf000091_0001
wherein a is 0, 1 , 2 or 3; or Z represents a group selected from Z-6, wherein Z-6 represents Z-6a, Z-6b, Z-6c or Z-6d:
Figure imgf000092_0001
(Z-6a) (Z-6b) (Z-6c) (Z-6d) wherein Y is Ci-4alkylene or C(R7)=C(R8);
R7 and R8 independently represent hydrogen, halogen, Ci C4alkyl, Ci C4haloalkyl or Ci- C4alkoxy; R9 represents hydrogen, d ealkyl, Cs ealkenyl, Cs ealkynyl, C3-6cycloalkyl, d ealkoxy, C(0)R10,
C(0)OR10, C(O)N(R 0)R11, S(0)2R10 or S(O)2N(R 0)R \ wherein Ci-6alkyl, C3-6alkenyl, C3-6alkynyl, C3- 6cycloalkyl and d ealkoxy are optionally substituted by halogen or cyano;
R 0 represents hydrogen, d ealkyl, d ecycloalkyl, d-6cycloalkyld-2alkyl, d-4alkoxyd-4alkyl, wherein d ealkyl, d ecycloalkyl, d-6cycloalkyld-2alkyl and d-4alkoxyd-4alkyl are optionally substituted by halogen or cyano; and
R represents hydrogen, d-4alkyl, d-4haloalkyl, d-4alkoxy or d-4alkoxyd-4alkyl; or a salt or an N-oxide thereof.
2. A compound according to claim 1 , wherein:
(i) A1 is CR and R is hydrogen, and A2 is CR2 and R2 is hydrogen;
(ii) A1 is CR1 and R is halogen, and A2 is CR2 and R2 is hydrogen; or
(iii) A1 is N and A2 is CR2 and R2 is hydrogen.
3. A compound according to claim 1 or claim 2, wherein A1 to A4 are C-H.
4. A compound according to any one of claims 1 to 3, wherein R5 and R6 are hydrogen, or R5 is hydrogen and R6 is methyl, or R5 and R6 are methyl.
5. A compound according to any one of claims 1 to 4, wherein Z is:
Z-1 wherein B and B2 represent C(R7)(R8); Z-2 wherein B\ B2 and B3 independently represent C(R7)(R8), O, NR9 or C(=0), wherein only one of B\ B2 and B3 may be O, NR9 or C(=0);
Z-3 wherein B , B2, B3 and B4 independently represent C(R7)(R8), O, NR9 or C(=0), wherein 5 only one of B\ B2, B3 and B4 may be O, NR9 or C(=0);
Z-6a wherein Y represents C(R7)=C(R8); or Z-6c wherein Y represents C2-4alkylene.
10
6. A compound according to claim 5, wherein Z is:
Z-2 wherein B and B3 independently represent C(R7)(R8), O, NR9 or C(=0), wherein only one of B and B3 may be a O, NR9 or C(=0), and B2 represents C(R7)(R8);
15
Z-3 wherein B\ B2 and B4 independently represent C(R7)(R8), O, NR9 or C(=0), wherein only one of B\ B2 and B4 may be a O, NR9 or C(=0), and B3 represents C(R7)(R8).
7. A compound according to claim 6, wherein Z is:
20
Z-2 wherein B and B3 independently represent C(R7)(R8), O or C(=0) wherein only one of B and B3 may be O or C(=0), and B2 represents C(R7)(R8), wherein R7 and R8, independently of each other, are selected from hydrogen or Ci- 4alkyl; or
25 Z-3 wherein B\ B2 and B4 independently represent C(R7)(R8), O, NR9 or C(=0) wherein only one of B\ B2 and B4 may be a O, NR9 or C(=0), and B3 represents C(R7)(R8), wherein R7 and R8, independently of each other, are selected from hydrogen or Ci- 4alkyl.
8. A compound according to any one of claims 1 to 6, wherein R7 and R8 independently 30 represent hydrogen, methyl, difluoromethyl, trifluoromethyl or methoxy.
9. A compound according to any one of claims 1 to 8, wherein R7 and R8 independently represent hydrogen or methyl.
35 10. A compound according to any one of claims 1 to 9, wherein n is 1.
11. A compound according to any one of claims 1 to 10, wherein X is C(O).
12. An agrochemical composition comprising a fungicidally effective amount of a compound of 40 formula (I) according to any one of claims 1 to 11.
13. The 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 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.
PCT/EP2016/079329 2015-12-02 2016-11-30 Microbiocidal oxadiazole derivatives WO2017093348A1 (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
US15/780,007 US10640497B2 (en) 2015-12-02 2016-11-30 Microbiocidal oxadiazole derivatives
BR112018011053A BR112018011053A2 (en) 2015-12-02 2016-11-30 microbiocidal oxadiazole derivatives
EP16802115.2A EP3383179B1 (en) 2015-12-02 2016-11-30 Microbiocidal oxadiazole derivatives
ES16802115T ES2810752T3 (en) 2015-12-02 2016-11-30 Oxadiazole derivatives microbicides
DK16802115.2T DK3383179T3 (en) 2015-12-02 2016-11-30 MICROBIOCIDE OXADIAZOLE DERIVATIVES
CN201680070488.2A CN108289448B (en) 2015-12-02 2016-11-30 Microbicidal oxadiazole derivatives
SI201630875T SI3383179T1 (en) 2015-12-02 2016-11-30 Microbiocidal oxadiazole derivatives
JP2018528660A JP6930972B2 (en) 2015-12-02 2016-11-30 Microbial oxadiazole derivative
MX2018006474A MX2018006474A (en) 2015-12-02 2016-11-30 Microbiocidal oxadiazole derivatives.
PL16802115T PL3383179T3 (en) 2015-12-02 2016-11-30 Microbiocidal oxadiazole derivatives
ZA2018/02969A ZA201802969B (en) 2015-12-02 2018-05-07 Microbiocidal oxadiazole derivatives
IL259695A IL259695B (en) 2015-12-02 2018-05-30 Microbiocidal oxadiazole derivatives
CONC2018/0005793A CO2018005793A2 (en) 2015-12-02 2018-06-01 Oxadiazole derivatives microbicides

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
EP15197571 2015-12-02
EPEP15197571.1 2015-12-02
EP15202192 2015-12-22
EPEP15202192.9 2015-12-22
EP16157729 2016-02-26
EPEP16157729.1 2016-02-26

Publications (1)

Publication Number Publication Date
WO2017093348A1 true WO2017093348A1 (en) 2017-06-08

Family

ID=57421885

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2016/079329 WO2017093348A1 (en) 2015-12-02 2016-11-30 Microbiocidal oxadiazole derivatives

Country Status (11)

Country Link
US (1) US10640497B2 (en)
JP (1) JP6930972B2 (en)
CN (1) CN108289448B (en)
BR (1) BR112018011053A2 (en)
CL (1) CL2018001469A1 (en)
CO (1) CO2018005793A2 (en)
IL (1) IL259695B (en)
MX (1) MX2018006474A (en)
UY (1) UY36999A (en)
WO (1) WO2017093348A1 (en)
ZA (1) ZA201802969B (en)

Cited By (171)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018187553A1 (en) * 2017-04-06 2018-10-11 Fmc Corporation Fungicidal oxadiazoles
WO2018219825A1 (en) * 2017-06-02 2018-12-06 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018219773A1 (en) * 2017-06-02 2018-12-06 Syngenta Participations Ag Fungicidal compositions
WO2018228896A1 (en) 2017-06-14 2018-12-20 Syngenta Participations Ag Fungicidal compositions
WO2019002158A1 (en) 2017-06-30 2019-01-03 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
WO2019012003A1 (en) * 2017-07-13 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019011929A1 (en) * 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019012001A1 (en) * 2017-07-12 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019011928A1 (en) * 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019011926A1 (en) * 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019011923A1 (en) * 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019012011A1 (en) * 2017-07-12 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019020501A1 (en) 2017-07-28 2019-01-31 Basf Se Preparation of substituted 3-aryl-5-trifluoromethyl-1,2,4-oxadiazoles
WO2019022061A1 (en) 2017-07-27 2019-01-31 日本曹達株式会社 Oxadiazole compound and fungicide for agricultural and horticultural use
US20190185462A1 (en) * 2016-06-23 2019-06-20 Merck Sharp & Dohme Corp. 3-aryl- heteroaryl substituted 5-trifluoromethyl oxadiazoles as histonedeacetylase 6 (hdac6) inhibitors
WO2019150219A2 (en) 2018-01-30 2019-08-08 Pi Industries Ltd. Novel oxadiazoles
WO2019171234A1 (en) 2018-03-09 2019-09-12 Pi Industries Ltd. Heterocyclic compounds as fungicides
WO2019224160A1 (en) 2018-05-25 2019-11-28 Syngenta Participations Ag Microbiocidal picolinamide derivatives
US10501425B2 (en) 2015-10-02 2019-12-10 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2020025807A1 (en) 2018-08-03 2020-02-06 Syngenta Crop Protection Ag Microbiocidal 1,2,5-oxadiazol-3(2h)-one derivatives
WO2020053365A2 (en) 2018-09-13 2020-03-19 Syngenta Participations Ag Pesticidally active azole-amide compounds
WO2020053364A1 (en) 2018-09-13 2020-03-19 Syngenta Participations Ag Pesticidally active azole-amide compounds
WO2020070611A1 (en) 2018-10-01 2020-04-09 Pi Industries Ltd Oxadiazoles as fungicides
WO2020070610A1 (en) 2018-10-01 2020-04-09 Pi Industries Ltd. Novel oxadiazoles
WO2020079198A1 (en) 2018-10-19 2020-04-23 Syngenta Participations Ag Pesticidally active azole-amide compounds
WO2020079111A1 (en) 2018-10-18 2020-04-23 Syngenta Crop Protection Ag Microbiocidal compounds
WO2020094363A1 (en) 2018-11-05 2020-05-14 Syngenta Participations Ag Pesticidally active azole-amide compounds
WO2020109511A1 (en) 2018-11-30 2020-06-04 Syngenta Crop Protection Ag Microbiocidal 2-acylamino-thiazole-4-carboxamide derivatives
WO2020109509A1 (en) 2018-11-30 2020-06-04 Syngenta Participations Ag Microbiocidal thiazole derivatives
WO2020165403A1 (en) 2019-02-15 2020-08-20 Syngenta Crop Protection Ag Phenyl substituted thiazole derivatives as microbiocidal compounds
WO2020169526A1 (en) 2019-02-18 2020-08-27 Syngenta Crop Protection Ag Pesticidally-active cyanamide heterocyclic compounds
WO2020169445A1 (en) 2019-02-18 2020-08-27 Syngenta Crop Protection Ag Pesticidally active azole-amide compounds
WO2020182649A1 (en) 2019-03-08 2020-09-17 Syngenta Crop Protection Ag Pesticidally active azole-amide compounds
WO2020188014A1 (en) 2019-03-20 2020-09-24 Syngenta Crop Protection Ag Pesticidally active azole amide compounds
WO2020188027A1 (en) 2019-03-20 2020-09-24 Syngenta Crop Protection Ag Pesticidally active azole amide compounds
WO2020193341A1 (en) 2019-03-22 2020-10-01 Syngenta Crop Protection Ag N-[1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-2-cyclopropyl-6-(trifluoromethyl)pyridine-4-carboxamide derivatives and related compounds as insecticides
WO2020193387A1 (en) 2019-03-22 2020-10-01 Syngenta Crop Protection Ag Fungicidal compounds
WO2020193618A1 (en) 2019-03-27 2020-10-01 Syngenta Crop Protection Ag Microbiocidal thiazole derivatives
WO2020201398A1 (en) 2019-04-05 2020-10-08 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2020201079A1 (en) 2019-03-29 2020-10-08 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
US10798941B2 (en) 2016-01-08 2020-10-13 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2020208096A1 (en) 2019-04-10 2020-10-15 Syngenta Crop Protection Ag Fungicidal compositions
WO2020208036A1 (en) 2019-04-11 2020-10-15 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2020208095A1 (en) 2019-04-10 2020-10-15 Syngenta Crop Protection Ag Microbiocidal picolinamide derivatives
WO2020239855A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2020239853A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2020239856A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2020239854A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2020254530A1 (en) 2019-06-18 2020-12-24 Syngenta Crop Protection Ag 7-sulfonyl-n-(1,3,4-thiadiazol-2-yl)-quinoxaline-6-carboxamide derivatives and the respective -benzimidazole-5-, -imidazo[4,5-b]pyridine-5-, -3h-furo[3,2b]pyridine-5-, -quinoline-2-, and -naphthalene-2-carboxamide derivatives as pesticides
WO2021004968A1 (en) 2019-07-05 2021-01-14 Syngenta Crop Protection Ag Microbiocidal picolinamide derivatives
WO2021009026A1 (en) 2019-07-12 2021-01-21 Syngenta Crop Protection Ag Methyl 2-[(4-methoxyimino-tetralin-6-yl]prop-2-enoate derivatives, chromane, isochromane, 6,7,8,9-tetrahydrobenzo[7]annulene, 1h-isobenzofurane and indane analogues thereof, and similar compounds, as agrochemical fungicides
WO2021033133A1 (en) 2019-08-19 2021-02-25 Pi Industries Ltd. Novel oxadiazole compounds containing 5- membered heteroaromatic ring for controlling or preventing phytopathogenic fungi
WO2021032632A1 (en) 2019-08-21 2021-02-25 Syngenta Participations Ag Apparatus and method for converting existing sowing equipment
WO2021032633A1 (en) 2019-08-21 2021-02-25 Syngenta Participations Ag High precision greenhouse seed and seedling treatment
WO2021032634A1 (en) 2019-08-21 2021-02-25 Syngenta Participations Ag Apparatus and method for reducing dust development in precision drill sowing
WO2021032631A1 (en) 2019-08-21 2021-02-25 Syngenta Participations Ag Precision treatment and sowing or planting method and device
WO2021032630A1 (en) 2019-08-21 2021-02-25 Syngenta Participations Ag Sowing device and method for treating seeds during planting
WO2021037614A1 (en) 2019-08-23 2021-03-04 Syngenta Crop Protection Ag Pesticidally active pyrazine-amide compounds
WO2021043616A1 (en) 2019-09-02 2021-03-11 Syngenta Crop Protection Ag Strigolactone derivatives as plant growth regulator compounds
WO2021053110A1 (en) 2019-09-20 2021-03-25 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur and sulfoximine containing substituents
WO2021053161A1 (en) 2019-09-20 2021-03-25 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2021083936A1 (en) 2019-11-01 2021-05-06 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2021100745A1 (en) * 2019-11-21 2021-05-27 日本曹達株式会社 Oxadiazole compound and germicide for agricultural and horticultural use
WO2021110891A1 (en) 2019-12-04 2021-06-10 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic amino compounds
WO2021122645A1 (en) 2019-12-20 2021-06-24 Syngenta Crop Protection Ag Pesticidally active azole-amide compounds
WO2021136722A1 (en) 2019-12-31 2021-07-08 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021140122A1 (en) 2020-01-06 2021-07-15 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021144354A1 (en) 2020-01-15 2021-07-22 Syngenta Crop Protection Ag Pesticidally-active bicyclic heteroaromatic compounds
WO2021148639A1 (en) 2020-01-24 2021-07-29 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2021151926A1 (en) 2020-01-30 2021-08-05 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic amino compounds
WO2021160680A1 (en) 2020-02-11 2021-08-19 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2021170881A1 (en) 2020-02-27 2021-09-02 Syngenta Crop Protection Ag Pesticidally active diazine-bisamide compounds
WO2021176057A1 (en) 2020-03-05 2021-09-10 Syngenta Crop Protection Ag Fungicidal compositions
WO2021175822A1 (en) 2020-03-02 2021-09-10 Syngenta Crop Protection Ag Pesticidally amidine-substituted benzoic acid amide compounds
WO2021176007A1 (en) 2020-03-05 2021-09-10 Syngenta Crop Protection Ag Fungicidal compositions
WO2021180596A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021180592A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021180598A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021180974A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021180976A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola, cercospora sojina and/or cercospora kikuchii
WO2021180975A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021204857A1 (en) 2020-04-08 2021-10-14 Syngenta Crop Protection Ag Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives
WO2021204822A1 (en) 2020-04-08 2021-10-14 Syngenta Crop Protection Ag Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives
WO2021204855A1 (en) 2020-04-08 2021-10-14 Syngenta Crop Protection Ag Microbiocidal quinoline dihydropyrrolopyrazine derivatives
WO2021213929A1 (en) 2020-04-20 2021-10-28 Syngenta Crop Protection Ag Pesticidally active substituted 1,3-dihydro-2h-imidazo[4,5-c]pyridin-2-one derivatives with sulfur containing substituents
WO2021219810A1 (en) 2020-04-30 2021-11-04 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021219775A1 (en) 2020-04-30 2021-11-04 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021219778A1 (en) 2020-04-30 2021-11-04 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021219780A1 (en) 2020-05-01 2021-11-04 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021224409A1 (en) 2020-05-06 2021-11-11 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021224102A1 (en) 2020-05-05 2021-11-11 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021244952A1 (en) 2020-06-03 2021-12-09 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2021244950A1 (en) 2020-06-03 2021-12-09 Syngenta Crop Protection Ag Fungicidal compositions
WO2021244951A1 (en) 2020-06-03 2021-12-09 Syngenta Crop Protection Ag Fungicidal compositions
WO2021251274A1 (en) 2020-06-08 2021-12-16 日本曹達株式会社 Method for reducing or preventing effect of non-biological stress on plant
WO2022013417A1 (en) 2020-07-17 2022-01-20 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022017975A1 (en) 2020-07-18 2022-01-27 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022043576A2 (en) 2020-08-31 2022-03-03 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022049146A1 (en) 2020-09-02 2022-03-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022049141A1 (en) 2020-09-01 2022-03-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022048988A1 (en) 2020-09-02 2022-03-10 Syngenta Participations Ag Plant growth regulator compounds
WO2022049144A1 (en) 2020-09-02 2022-03-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022053567A1 (en) 2020-09-09 2022-03-17 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022058580A1 (en) 2020-09-21 2022-03-24 Syngenta Crop Protection Ag Microbiocidal compounds
WO2022084346A1 (en) 2020-10-22 2022-04-28 Syngenta Crop Protection Ag Zealactone derivatives as plant growth regulators
WO2022101265A1 (en) 2020-11-13 2022-05-19 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2022117653A1 (en) 2020-12-02 2022-06-09 Syngenta Crop Protection Ag Fungicidal compositions
WO2022117650A1 (en) 2020-12-02 2022-06-09 Syngenta Crop Protection Ag Fungicidal compositions
WO2022157188A2 (en) 2021-01-23 2022-07-28 Syngenta Crop Protection Ag Pesticidally active heteroaromatic compounds
WO2022157334A1 (en) 2021-01-21 2022-07-28 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022157122A1 (en) 2021-01-22 2022-07-28 Syngenta Crop Protection Ag Method for the control or suppression of phytopathogenic bacteria
WO2022207665A1 (en) 2021-03-31 2022-10-06 Syngenta Crop Protection Ag Microbiocidal quinoline/quinoxaline benzothiazine derivatives
WO2022207479A1 (en) 2021-03-27 2022-10-06 Syngenta Crop Protection Ag Microbiocidal isonicotinic amide derivatives
WO2022207462A1 (en) 2021-03-30 2022-10-06 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2022219146A2 (en) 2021-04-16 2022-10-20 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2022223376A1 (en) 2021-04-20 2022-10-27 Syngenta Crop Protection Ag Microbiocidal quinoline/quinoxaline isoquinoline derivatives
WO2022233869A1 (en) 2021-05-04 2022-11-10 Syngenta Crop Protection Ag Use of clethodim for insect control
EP4094579A1 (en) * 2021-05-28 2022-11-30 Basf Se Pesticidal mixtures comprising metyltetraprole
WO2022253841A1 (en) 2021-06-02 2022-12-08 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfoximine containing substituents
WO2022253645A1 (en) 2021-06-01 2022-12-08 Syngenta Crop Protection Ag Microbiocidal tetrahydroisoquinoline derivatives
WO2022258481A1 (en) 2021-06-09 2022-12-15 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2022268648A1 (en) 2021-06-24 2022-12-29 Syngenta Crop Protection Ag 2-[3-[1 [(quinazolin-4-yl)amino]ethyl]pyrazin-2-yl]thiazole-5-carbonitrile derivatives and similar compounds as pesticides
WO2023275116A1 (en) 2021-07-02 2023-01-05 Syngenta Crop Protection Ag Use of fluazifop-p-butyl for insect control
WO2023006789A1 (en) 2021-07-29 2023-02-02 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2023006634A1 (en) 2021-07-27 2023-02-02 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023012081A1 (en) 2021-08-05 2023-02-09 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023012044A1 (en) 2021-08-02 2023-02-09 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2023017016A1 (en) 2021-08-10 2023-02-16 Syngenta Crop Protection Ag Fungicide mixture
WO2023017094A1 (en) 2021-08-10 2023-02-16 Syngenta Crop Protection Ag 2,2-difluoro-5h-[1,3]dioxolo[4,5-f]isoindol-7-one derivatives as pesticides
WO2023021020A1 (en) 2021-08-19 2023-02-23 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023061838A1 (en) 2021-10-14 2023-04-20 Syngenta Crop Protection Ag Imidazo[1,2-a]pyridine derivatives
WO2023072849A1 (en) 2021-10-27 2023-05-04 Syngenta Crop Protection Ag Pesticidally active pyridazinone compounds
WO2023072945A1 (en) 2021-10-25 2023-05-04 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023072785A1 (en) 2021-10-29 2023-05-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2023072784A1 (en) 2021-10-29 2023-05-04 Syngenta Crop Protection Ag Fungicidal compositions comprising fludioxonil
WO2023089049A2 (en) 2021-11-19 2023-05-25 Syngenta Crop Protection Ag Microbiocidal isonicotinic amide derivatives
WO2023094304A1 (en) 2021-11-25 2023-06-01 Syngenta Crop Protection Ag Microbiocidal heterobiaryl amide derivatives
WO2023094303A1 (en) 2021-11-25 2023-06-01 Syngenta Crop Protection Ag Microbiocidal heterobiaryl amide derivatives
WO2023099460A1 (en) 2021-12-02 2023-06-08 Syngenta Crop Protection Ag Fungicidal compositions
WO2023104714A1 (en) 2021-12-10 2023-06-15 Syngenta Crop Protection Ag Pesticidally active pyridazinone compounds
EP4197333A1 (en) 2021-12-15 2023-06-21 Syngenta Crop Protection AG Method for controlling diamide resistant pests & compounds therefor
WO2023110871A1 (en) 2021-12-17 2023-06-22 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2023111215A1 (en) 2021-12-17 2023-06-22 Syngenta Crop Protection Ag Microbiocidal pyridine-substituted benzothiazine derivatives
WO2023110710A1 (en) 2021-12-13 2023-06-22 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023110928A1 (en) 2021-12-17 2023-06-22 Syngenta Crop Protection Ag Fungicidal compositions
WO2023110869A1 (en) 2021-12-15 2023-06-22 Syngenta Crop Protection Ag Microbiocidal bicycle heterocyclic derivatives
WO2023117625A1 (en) 2021-12-22 2023-06-29 Syngenta Crop Protection Ag Fungicidal compositions
WO2023118011A1 (en) 2021-12-22 2023-06-29 Syngenta Crop Protection Ag Microbiocidal aza-heterobiaryl derivatives
WO2023118434A1 (en) 2021-12-22 2023-06-29 Globachem Nv Pesticidally active amide compounds
WO2023139166A1 (en) 2022-01-19 2023-07-27 Syngenta Crop Protection Ag Methods for controlling plant pathogens
WO2023148368A1 (en) 2022-02-07 2023-08-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023148206A1 (en) 2022-02-02 2023-08-10 Syngenta Crop Protection Ag Microbiocidal n-amide derivatives
WO2023148369A1 (en) 2022-02-07 2023-08-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023166067A1 (en) 2022-03-02 2023-09-07 Syngenta Crop Protection Ag Microbiocidal pyridazinone amide derivatives
WO2023187191A1 (en) 2022-04-01 2023-10-05 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023209238A1 (en) 2022-04-29 2023-11-02 Syngenta Crop Protection Ag Fungicidal compositions
WO2023217989A1 (en) 2022-05-12 2023-11-16 Syngenta Crop Protection Ag Alkoxy heteroaryl- carboxamide or thioamide compounds
WO2023247360A1 (en) 2022-06-21 2023-12-28 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2023247552A1 (en) 2022-06-21 2023-12-28 Syngenta Crop Protection Ag Microbiocidal bicyclic heterocyclic carboxamide derivatives
WO2024008567A1 (en) 2022-07-07 2024-01-11 Syngenta Crop Protection Ag Precision application devices and compositions
WO2024017788A1 (en) 2022-07-22 2024-01-25 Syngenta Crop Protection Ag Solid form of a heterocyclic amide derivative
WO2024018016A1 (en) 2022-07-21 2024-01-25 Syngenta Crop Protection Ag Crystalline forms of 1,2,4-oxadiazole fungicides
WO2024022910A1 (en) 2022-07-26 2024-02-01 Syngenta Crop Protection Ag 1-[1-[2-(pyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-3-[2,4-dichloro-5-phenyl]urea derivatives and similar compounds as pesticides
WO2024033374A1 (en) 2022-08-11 2024-02-15 Syngenta Crop Protection Ag Novel arylcarboxamide or arylthioamide compounds
WO2024038053A1 (en) 2022-08-16 2024-02-22 Syngenta Crop Protection Ag New use of pydiflumetofen
WO2024056732A1 (en) 2022-09-16 2024-03-21 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2024068950A1 (en) 2022-09-30 2024-04-04 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2024068838A1 (en) 2022-09-28 2024-04-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2024068656A1 (en) 2022-09-28 2024-04-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2024068655A1 (en) 2022-09-28 2024-04-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2024068947A1 (en) 2022-09-30 2024-04-04 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10640497B2 (en) * 2015-12-02 2020-05-05 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
JP2019537553A (en) * 2016-09-23 2019-12-26 シンジェンタ パーティシペーションズ アーゲー Microbicidal oxadiazole derivatives
CN113527338B (en) * 2021-06-30 2022-10-18 海南海灵化学制药有限公司 Synthesis process of cefozopran hydrochloride
WO2023154758A1 (en) * 2022-02-08 2023-08-17 Georgetown University A1h-benzo[c][1,2]thiadiazine-2,2-dioxides bearing heterocyclic linkers as selective histone deacetylase 6 inhibitors

Citations (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4639771A (en) 1984-10-31 1987-01-27 Kabushiki Kaisha Toshiba Image processing system
EP0357460A2 (en) 1988-09-02 1990-03-07 Sankyo Company Limited 13-Substituted milbemycin derivatives, their preparation and use
EP0367474A1 (en) 1988-11-01 1990-05-09 Mycogen Corporation Novel bacillus thuringiensis isolate denoted b.t. ps81gg, active against lepidopteran pests, and a gene encoding a lepidopteran-active toxin
EP0374753A2 (en) 1988-12-19 1990-06-27 American Cyanamid Company Insecticidal toxines, genes coding therefor, antibodies binding them, transgenic plant cells and plants expressing these toxines
EP0382173A2 (en) 1989-02-07 1990-08-16 Meiji Seika Kaisha Ltd. PF 1022 substance, method of producing same and anthelmintic composition containing same
WO1990013651A1 (en) 1989-05-09 1990-11-15 Imperial Chemical Industries Plc Bacterial genes
EP0401979A2 (en) 1989-05-18 1990-12-12 Mycogen Corporation Novel bacillus thuringiensis isolates active against lepidopteran pests, and genes encoding novel lepidopteran-active toxins
US5015630A (en) 1989-01-19 1991-05-14 Merck & Co., Inc. 5-oxime avermectin derivatives
EP0427529A1 (en) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Larvicidal lectins and plant insect resistance based thereon
EP0444964A1 (en) 1990-03-01 1991-09-04 Sankyo Company Limited Milbemycin ether derivatives, their preparation and their anthelmintic uses
EP0451878A1 (en) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modifying plants by genetic engineering to combat or control insects
EP0503538A1 (en) 1991-03-08 1992-09-16 Meiji Seika Kaisha Ltd. Medicinal composition containing an anthelmintic cyclic depsipeptide
WO1993007278A1 (en) 1991-10-04 1993-04-15 Ciba-Geigy Ag Synthetic dna sequence having enhanced insecticidal activity in maize
WO1993019053A1 (en) 1992-03-17 1993-09-30 Fujisawa Pharmaceutical Co., Ltd. Depsipeptide derivative, production thereof and use thereof
WO1993025543A2 (en) 1992-06-11 1993-12-23 Bayer Aktiengesellschaft Enniatines and enniatine derivates used to control endoparasites
EP0594291A1 (en) 1992-09-01 1994-04-27 Sankyo Company Limited Novel processes for the production of 13-ether derivatives of milbemycins, and novel intermediates therefor
WO1994015944A1 (en) 1993-01-18 1994-07-21 Pfizer Limited New antiparasitic agents related to the milbemycins and avermectins
WO1994019334A1 (en) 1993-02-19 1994-09-01 Meiji Seika Kaisha, Ltd. Pf1022 derivative, cyclic depsipeptide
EP0626375A1 (en) 1993-05-26 1994-11-30 Bayer Ag Octacyclodepsipeptides having endoparasiticidal activity
WO1995019363A1 (en) 1994-01-14 1995-07-20 Pfizer Inc. Antiparasitic pyrrolobenzoxazine compounds
WO1995022552A1 (en) 1994-02-16 1995-08-24 Pfizer Limited Antiparasitic agents
WO1995034656A1 (en) 1994-06-10 1995-12-21 Ciba-Geigy Ag Novel bacillus thuringiensis genes coding toxins active against lepidopteran pests
US5478855A (en) 1992-04-28 1995-12-26 Yashima Chemical Industry Co., Ltd. 2-(2,6-difluorophenyl)-4-(2-ethoxy-4-tert-butylphenyl)-2-oxazoline
WO1996011945A2 (en) 1994-10-18 1996-04-25 Bayer Aktiengesellschaft Cyclic depsipeptide sulfonylation, sulfenylation and phosphorylation process
WO1996015121A1 (en) 1994-11-10 1996-05-23 Bayer Aktiengesellschaft Use of dioxomorpholines to combat endoparasites, novel dioxomorpholines and process for their production
DE19520936A1 (en) 1995-06-08 1996-12-12 Bayer Ag Ectoparasiticides means
WO1997033890A1 (en) 1996-03-11 1997-09-18 Novartis Ag Pyrimidin-4-one derivatives as pesticide
WO2002015701A2 (en) 2000-08-25 2002-02-28 Syngenta Participations Ag Bacillus thuringiensis crystal protein hybrids
WO2003018810A2 (en) 2001-08-31 2003-03-06 Syngenta Participations Ag Modified cry3a toxins and nucleic acid sequences coding therefor
WO2003028729A2 (en) 2001-10-03 2003-04-10 Pharmacia Corporation Prodrugs of substituted polycyclic compounds useful for selective inhibition of the coagulation cascade
WO2003052073A2 (en) 2001-12-17 2003-06-26 Syngenta Participations Ag Novel corn event
WO2003087940A2 (en) 2002-04-09 2003-10-23 Day International, Inc. Printing elements and method for producing the same using digital imaging photopolymerization
WO2004072086A2 (en) 2003-02-14 2004-08-26 Pfizer Limited Antiparasitic terpene alkaloids
WO2004087646A2 (en) 2003-04-03 2004-10-14 Merck Patent Gmbh Pyrrolidino-1,2-dicarboxy-1-(phenylamide)-2-(4-(3-oxo-morpholino-4-yl)-phenylamide) derivatives and related compounds for use as inhibitors of coagulation factor xa in the treatment of thrombo-embolic diseases
US6919298B2 (en) 2002-04-04 2005-07-19 Valent Biosciences Corporation Enhanced herbicide composition
CN1927860A (en) * 2005-09-08 2007-03-14 国家南方农药创制中心江苏基地 Pyrazolecarboxamide compounds, intermediate thereof and pest control chemicals with the same as active component
US20070155739A1 (en) 2005-12-30 2007-07-05 Alantos Pharmaceuticals, Inc. Substituted bis-amide metalloprotease inhibitors
WO2008104306A2 (en) 2007-02-27 2008-09-04 Bayer Schering Pharma Aktiengesellschaft Substituted 4-aryl-1,4-dihydro-1,6-naphthyridinamides and use thereof
WO2009022746A1 (en) 2007-08-10 2009-02-19 Nippon Soda Co., Ltd. Nitrogen-containing heterocyclic compound and pest control agent
WO2010045251A2 (en) 2008-10-17 2010-04-22 Xenon Pharmaceuticals, Inc. Spiro-oxindole compounds and their use as therapeutic agents
WO2013066838A1 (en) 2011-10-31 2013-05-10 Glaxosmithkline Llc Compounds and methods
WO2013071232A1 (en) 2011-11-11 2013-05-16 Beta Cat Pharmaceuticals, Llc Compositions and methods for inhibition of tbl-1 binding to disease-associated molecules
WO2013132253A1 (en) 2012-03-07 2013-09-12 Institute Of Cancer Research: Royal Cancer Hospital (The) 3-aryl-5-substituted-isoquinolin-1-one compounds and their therapeutic use
WO2013156559A1 (en) * 2012-04-20 2013-10-24 Bayer Cropscience Ag N-cycloalkyl-n-[(heterocyclylphenyl)methylene]-(thio)carboxamide derivatives
WO2014020350A1 (en) 2012-08-01 2014-02-06 Proximagen Limited Par2 receptor antagonists

Family Cites Families (59)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4871753A (en) * 1986-12-12 1989-10-03 Ciba-Geigy Corporation 3-Phenyl-5-trifluoromethyl-1,2,4-oxadiazole compounds which are useful pesticides
ZA879329B (en) * 1986-12-12 1988-06-13 Ciba-Geigy Ag Pesticides
KR20010021645A (en) * 1997-07-11 2001-03-15 로렌스 티. 마이젠헬더 Thiadiazolyl and Oxadiazolyl Phenyl Oxazolidinone Antibacterial Agents
KR20050084621A (en) * 2002-11-15 2005-08-26 티보텍 파마슈티칼즈 리미티드 Substituted indolepyridium as anti-infective compounds
CL2007002787A1 (en) 2006-09-29 2008-05-30 Bayer Cropscience Sa COMPOUNDS DERIVED FROM N-CICLOALQUIL-CARBOXAMIDA, N-CICLOALQUIL-TIOCARBOXAMIDA AND N-CICLOALQUIL-CARBOXAMIDAMIDA N-SUBSTITUTED; FUNGICIDE COMPOSITION THAT INCLUDES SUCH COMPOUNDS; AND METHOD TO COMBAT FITOPATOGEN CULTURE FUNGIANS THAT YOU UNDERSTAND
WO2009086303A2 (en) * 2007-12-21 2009-07-09 University Of Rochester Method for altering the lifespan of eukaryotic organisms
CN103221047B (en) 2010-01-13 2014-12-17 坦颇罗制药股份有限公司 Compounds and methods
WO2011088192A1 (en) 2010-01-13 2011-07-21 Tempero Pharmaceuticals, Inc. Compounds and methods
ES2543747T3 (en) 2010-02-17 2015-08-21 Syngenta Participations Ag Isoxazoline derivatives as insecticides
CA2815105A1 (en) 2010-10-21 2012-04-26 Bayer Intellectual Property Gmbh N-benzyl heterocyclic carboxamides
WO2013006408A1 (en) 2011-07-01 2013-01-10 Tempero Pharmaceuticals, Inc. Compounds and methods
ES2556822T3 (en) 2011-07-08 2016-01-20 Novartis Ag Novel trifluoromethyl-oxadiazole derivatives and their use in the treatment of disease
WO2013009810A1 (en) 2011-07-13 2013-01-17 Tempero Pharmaceuticals, Inc. Methods of treatment
WO2013009830A1 (en) 2011-07-13 2013-01-17 Tempero Pharmaceuticals, Inc. Methods of treatment
WO2013009827A1 (en) 2011-07-13 2013-01-17 Tempero Pharmaceuticals, Inc. Methods of treatment
WO2013066835A2 (en) 2011-10-31 2013-05-10 Glaxosmithkline Llc Compounds and methods
WO2013066839A2 (en) 2011-10-31 2013-05-10 Glaxosmithkline Llc Compounds and methods
CN103081916B (en) 2011-11-02 2014-08-06 中国中化股份有限公司 Application of pyrazole amide compound as agricultural bactericide
CA2856334A1 (en) 2011-11-28 2013-06-06 Christina Hebach Novel trifluoromethyl-oxadiazole derivatives and their use in the treatment of disease
WO2015055706A2 (en) 2013-10-16 2015-04-23 Bayer Cropscience Ag N-cycloalkyl-n-(biheterocyclymethylene)-(thio)carboxamide derivatives
CN106455572B (en) 2014-06-06 2020-01-14 巴斯夫欧洲公司 Use of substituted oxadiazoles for combating phytopathogenic fungi
JP6556146B2 (en) 2014-08-26 2019-08-07 武田薬品工業株式会社 Heterocyclic compounds
JP2016190828A (en) * 2015-03-31 2016-11-10 日本ゼオン株式会社 Method for producing polymerizable compound
EP3342772A4 (en) 2015-08-25 2019-03-27 Takeda Pharmaceutical Company Limited Heterocyclic compound
WO2017055473A1 (en) * 2015-10-02 2017-04-06 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
JP6864673B2 (en) * 2015-10-02 2021-04-28 シンジェンタ パーティシペーションズ アーゲー Microbial oxadiazole derivative
EP3367798A1 (en) * 2015-10-28 2018-09-05 Syngenta Participations AG Microbiocidal oxadiazole derivatives
US20190135798A1 (en) 2015-11-02 2019-05-09 Basf Se Substituted Oxadiazoles for Combating Phytopathogenic Fungi
EP3371155A1 (en) 2015-11-03 2018-09-12 Basf Se Use of substituted oxadiazoles for combating phytopathogenic fungi
EP3165094A1 (en) 2015-11-03 2017-05-10 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
BR112018008288A2 (en) 2015-11-04 2018-10-30 Basf Se use of formula compounds, formula compounds, mixture, agrochemical composition and method for combating fungi
WO2017076935A1 (en) 2015-11-04 2017-05-11 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
CR20180310A (en) 2015-11-05 2018-11-30 Basf Se OXADIAZOLS REPLACED TO COMBAT HONGOD PHYTOOPATHOGENS
EP3165093A1 (en) 2015-11-05 2017-05-10 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
AR106679A1 (en) 2015-11-13 2018-02-07 Basf Se OXADIAZOLS REPLACED TO FIGHT FITOPATHOGEN FUNGI
BR112018009579A2 (en) 2015-11-13 2018-11-06 Basf Se compound of formula i, mixture, agrochemical composition, compound use and fungal control method
WO2017081309A1 (en) 2015-11-13 2017-05-18 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
BR112018009566A2 (en) 2015-11-13 2018-11-06 Basf Se compounds, mixture, agrochemical composition, use of compounds and method to combat phytopathogenic harmful fungi
WO2017085100A1 (en) * 2015-11-19 2017-05-26 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2017085098A1 (en) 2015-11-19 2017-05-26 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
US10640497B2 (en) * 2015-12-02 2020-05-05 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2017093019A1 (en) 2015-12-03 2017-06-08 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
JP2019507110A (en) * 2015-12-17 2019-03-14 シンジェンタ パーティシペーションズ アーゲー Microbicidal oxadiazole derivative
JP2019504828A (en) * 2015-12-22 2019-02-21 シンジェンタ パーティシペーションズ アーゲー Microbicidal oxadiazole derivatives
WO2017110864A1 (en) 2015-12-25 2017-06-29 住友化学株式会社 Plant disease control composition and application for same
JP6841234B2 (en) 2015-12-25 2021-03-10 住友化学株式会社 Oxadiazole compounds and their uses
WO2017110861A1 (en) 2015-12-25 2017-06-29 住友化学株式会社 Plant disease control agent containing oxadiazole compound
WO2017110862A1 (en) 2015-12-25 2017-06-29 住友化学株式会社 Oxadiazole compound and use thereof
WO2017111152A1 (en) 2015-12-25 2017-06-29 住友化学株式会社 Oxadiazole compounds and use thereof
WO2017148797A1 (en) * 2016-03-01 2017-09-08 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2017169893A1 (en) 2016-03-31 2017-10-05 住友化学株式会社 Oxadiazole compound and use thereof
CA3020532A1 (en) 2016-04-11 2017-10-19 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
JP2017190296A (en) 2016-04-13 2017-10-19 住友化学株式会社 Pest control composition and use therefor
BR112018074569B1 (en) 2016-06-09 2022-10-04 Basf Se COMPOUNDS, USE OF N-(2,4-DIFLUOROPHENYL)-4-[5-(TRIFLUOROMETHYL)-1,2,4-OXADIAZOLE-3-YL] BENZAMIDE, AGROCHEMICAL COMPOSITION AND METHOD TO FIGHT HARMFUL PHYTOPATOGENIC FUNGI
WO2017211649A1 (en) 2016-06-09 2017-12-14 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
BR112018074559A2 (en) 2016-06-09 2019-03-12 Basf Se compounds, agrochemical composition, use of compounds and method to combat phytopathogenic harmful fungi
WO2017213252A1 (en) 2016-06-10 2017-12-14 Sumitomo Chemical Company, Limited Oxadiazole compound and use as pesticide
US11066396B2 (en) 2016-06-23 2021-07-20 Merck Sharp & Dohme Corp. 3-aryl- heteroaryl substituted 5-trifluoromethyl oxadiazoles as histonedeacetylase 6 (HDAC6) inhibitors
AR109304A1 (en) 2016-08-10 2018-11-21 Sumitomo Chemical Co OXADIAZOL COMPOUND AND ITS USE

Patent Citations (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4639771A (en) 1984-10-31 1987-01-27 Kabushiki Kaisha Toshiba Image processing system
EP0451878A1 (en) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modifying plants by genetic engineering to combat or control insects
EP0357460A2 (en) 1988-09-02 1990-03-07 Sankyo Company Limited 13-Substituted milbemycin derivatives, their preparation and use
EP0367474A1 (en) 1988-11-01 1990-05-09 Mycogen Corporation Novel bacillus thuringiensis isolate denoted b.t. ps81gg, active against lepidopteran pests, and a gene encoding a lepidopteran-active toxin
EP0374753A2 (en) 1988-12-19 1990-06-27 American Cyanamid Company Insecticidal toxines, genes coding therefor, antibodies binding them, transgenic plant cells and plants expressing these toxines
US5015630A (en) 1989-01-19 1991-05-14 Merck & Co., Inc. 5-oxime avermectin derivatives
EP0382173A2 (en) 1989-02-07 1990-08-16 Meiji Seika Kaisha Ltd. PF 1022 substance, method of producing same and anthelmintic composition containing same
WO1990013651A1 (en) 1989-05-09 1990-11-15 Imperial Chemical Industries Plc Bacterial genes
EP0401979A2 (en) 1989-05-18 1990-12-12 Mycogen Corporation Novel bacillus thuringiensis isolates active against lepidopteran pests, and genes encoding novel lepidopteran-active toxins
EP0427529A1 (en) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Larvicidal lectins and plant insect resistance based thereon
EP0444964A1 (en) 1990-03-01 1991-09-04 Sankyo Company Limited Milbemycin ether derivatives, their preparation and their anthelmintic uses
EP0503538A1 (en) 1991-03-08 1992-09-16 Meiji Seika Kaisha Ltd. Medicinal composition containing an anthelmintic cyclic depsipeptide
WO1993007278A1 (en) 1991-10-04 1993-04-15 Ciba-Geigy Ag Synthetic dna sequence having enhanced insecticidal activity in maize
WO1993019053A1 (en) 1992-03-17 1993-09-30 Fujisawa Pharmaceutical Co., Ltd. Depsipeptide derivative, production thereof and use thereof
US5478855A (en) 1992-04-28 1995-12-26 Yashima Chemical Industry Co., Ltd. 2-(2,6-difluorophenyl)-4-(2-ethoxy-4-tert-butylphenyl)-2-oxazoline
WO1993025543A2 (en) 1992-06-11 1993-12-23 Bayer Aktiengesellschaft Enniatines and enniatine derivates used to control endoparasites
EP0594291A1 (en) 1992-09-01 1994-04-27 Sankyo Company Limited Novel processes for the production of 13-ether derivatives of milbemycins, and novel intermediates therefor
WO1994015944A1 (en) 1993-01-18 1994-07-21 Pfizer Limited New antiparasitic agents related to the milbemycins and avermectins
WO1994019334A1 (en) 1993-02-19 1994-09-01 Meiji Seika Kaisha, Ltd. Pf1022 derivative, cyclic depsipeptide
EP0626375A1 (en) 1993-05-26 1994-11-30 Bayer Ag Octacyclodepsipeptides having endoparasiticidal activity
WO1995019363A1 (en) 1994-01-14 1995-07-20 Pfizer Inc. Antiparasitic pyrrolobenzoxazine compounds
WO1995022552A1 (en) 1994-02-16 1995-08-24 Pfizer Limited Antiparasitic agents
WO1995034656A1 (en) 1994-06-10 1995-12-21 Ciba-Geigy Ag Novel bacillus thuringiensis genes coding toxins active against lepidopteran pests
WO1996011945A2 (en) 1994-10-18 1996-04-25 Bayer Aktiengesellschaft Cyclic depsipeptide sulfonylation, sulfenylation and phosphorylation process
WO1996015121A1 (en) 1994-11-10 1996-05-23 Bayer Aktiengesellschaft Use of dioxomorpholines to combat endoparasites, novel dioxomorpholines and process for their production
DE19520936A1 (en) 1995-06-08 1996-12-12 Bayer Ag Ectoparasiticides means
WO1997033890A1 (en) 1996-03-11 1997-09-18 Novartis Ag Pyrimidin-4-one derivatives as pesticide
WO2002015701A2 (en) 2000-08-25 2002-02-28 Syngenta Participations Ag Bacillus thuringiensis crystal protein hybrids
WO2003018810A2 (en) 2001-08-31 2003-03-06 Syngenta Participations Ag Modified cry3a toxins and nucleic acid sequences coding therefor
WO2003028729A2 (en) 2001-10-03 2003-04-10 Pharmacia Corporation Prodrugs of substituted polycyclic compounds useful for selective inhibition of the coagulation cascade
WO2003052073A2 (en) 2001-12-17 2003-06-26 Syngenta Participations Ag Novel corn event
US6919298B2 (en) 2002-04-04 2005-07-19 Valent Biosciences Corporation Enhanced herbicide composition
WO2003087940A2 (en) 2002-04-09 2003-10-23 Day International, Inc. Printing elements and method for producing the same using digital imaging photopolymerization
WO2004072086A2 (en) 2003-02-14 2004-08-26 Pfizer Limited Antiparasitic terpene alkaloids
WO2004087646A2 (en) 2003-04-03 2004-10-14 Merck Patent Gmbh Pyrrolidino-1,2-dicarboxy-1-(phenylamide)-2-(4-(3-oxo-morpholino-4-yl)-phenylamide) derivatives and related compounds for use as inhibitors of coagulation factor xa in the treatment of thrombo-embolic diseases
CN1927860A (en) * 2005-09-08 2007-03-14 国家南方农药创制中心江苏基地 Pyrazolecarboxamide compounds, intermediate thereof and pest control chemicals with the same as active component
US20070155739A1 (en) 2005-12-30 2007-07-05 Alantos Pharmaceuticals, Inc. Substituted bis-amide metalloprotease inhibitors
WO2008104306A2 (en) 2007-02-27 2008-09-04 Bayer Schering Pharma Aktiengesellschaft Substituted 4-aryl-1,4-dihydro-1,6-naphthyridinamides and use thereof
WO2009022746A1 (en) 2007-08-10 2009-02-19 Nippon Soda Co., Ltd. Nitrogen-containing heterocyclic compound and pest control agent
WO2010045251A2 (en) 2008-10-17 2010-04-22 Xenon Pharmaceuticals, Inc. Spiro-oxindole compounds and their use as therapeutic agents
WO2013066838A1 (en) 2011-10-31 2013-05-10 Glaxosmithkline Llc Compounds and methods
WO2013071232A1 (en) 2011-11-11 2013-05-16 Beta Cat Pharmaceuticals, Llc Compositions and methods for inhibition of tbl-1 binding to disease-associated molecules
WO2013132253A1 (en) 2012-03-07 2013-09-12 Institute Of Cancer Research: Royal Cancer Hospital (The) 3-aryl-5-substituted-isoquinolin-1-one compounds and their therapeutic use
WO2013156559A1 (en) * 2012-04-20 2013-10-24 Bayer Cropscience Ag N-cycloalkyl-n-[(heterocyclylphenyl)methylene]-(thio)carboxamide derivatives
WO2014020350A1 (en) 2012-08-01 2014-02-06 Proximagen Limited Par2 receptor antagonists

Non-Patent Citations (11)

* Cited by examiner, † Cited by third party
Title
"The Pesticide Manual", 2009, BRITISH CROP PROTECTION COUNCIL
A. ALBINI; S. PIETRA: "Heterocyclic N-oxides", 1991, CRC PRESS
GARCIA, M. ET AL., ORG. BIOMOL. CHEM., vol. 11, 2004, pages 1633
GUYONNER, M.; BAUDOIN, O., ORG. LETT., vol. 14, 2012, pages 398
KITAMURA, S. ET AL., CHEM. PHARM. BULL., vol. 49, 2001, pages 268
KOMPELLA, A ET AL., BIOORG. MED. CHEM. LETT., vol. 1, 2001, pages 3161
KOMPELLA, A. ET AL., ORG. PROC. RES. DEV., vol. 16, 2012, pages 1794
LIU, H. ET AL., BIOORG. MED. CHEM., vol. 16, 2008, pages 10013
LIU, S. ET AL., SYNTHESIS, vol. 14, 2001, pages 2078
PHILIPPS, D. P ET AL., TETRAHEDRON LETT., vol. 50, 2009, pages 7293
PHILIPPS, D. P. ET AL., TETRAHEDRON LETT., vol. 50, 2009, pages 7293

Cited By (183)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10501425B2 (en) 2015-10-02 2019-12-10 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
US11259524B2 (en) 2016-01-08 2022-03-01 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
US10798941B2 (en) 2016-01-08 2020-10-13 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
EP3475275A4 (en) * 2016-06-23 2020-01-22 Merck Sharp & Dohme Corp. 3-aryl and heteroaryl substituted 5-trifluoromethyl oxadiazoles as histone deacetylase 6 (hdac6) inhibitors
US11066396B2 (en) 2016-06-23 2021-07-20 Merck Sharp & Dohme Corp. 3-aryl- heteroaryl substituted 5-trifluoromethyl oxadiazoles as histonedeacetylase 6 (HDAC6) inhibitors
US20190185462A1 (en) * 2016-06-23 2019-06-20 Merck Sharp & Dohme Corp. 3-aryl- heteroaryl substituted 5-trifluoromethyl oxadiazoles as histonedeacetylase 6 (hdac6) inhibitors
WO2018187553A1 (en) * 2017-04-06 2018-10-11 Fmc Corporation Fungicidal oxadiazoles
US11708358B2 (en) 2017-04-06 2023-07-25 Fmc Corporation Fungicidal oxadiazoles
EP3957636A1 (en) * 2017-04-06 2022-02-23 FMC Corporation Fungicidal oxadiazoles
AU2018249537B2 (en) * 2017-04-06 2022-03-31 Fmc Corporation Fungicidal oxadiazoles
JP7235672B2 (en) 2017-04-06 2023-03-08 エフ エム シー コーポレーション fungicidal oxadiazole
JP2020516598A (en) * 2017-04-06 2020-06-11 エフ エム シー コーポレーションＦｍｃ Ｃｏｒｐｏｒａｔｉｏｎ Fungicidal oxadiazole
US11447481B2 (en) 2017-06-02 2022-09-20 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018219773A1 (en) * 2017-06-02 2018-12-06 Syngenta Participations Ag Fungicidal compositions
WO2018219825A1 (en) * 2017-06-02 2018-12-06 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018228896A1 (en) 2017-06-14 2018-12-20 Syngenta Participations Ag Fungicidal compositions
WO2019002158A1 (en) 2017-06-30 2019-01-03 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
WO2019011926A1 (en) * 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019011929A1 (en) * 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019011928A1 (en) * 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019011923A1 (en) * 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019012011A1 (en) * 2017-07-12 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019012001A1 (en) * 2017-07-12 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019012003A1 (en) * 2017-07-13 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
KR20200033256A (en) 2017-07-27 2020-03-27 닛뽕소다 가부시키가이샤 Oxadiazole compounds and fungicides for agricultural and horticultural use
WO2019022061A1 (en) 2017-07-27 2019-01-31 日本曹達株式会社 Oxadiazole compound and fungicide for agricultural and horticultural use
US11365193B2 (en) 2017-07-27 2022-06-21 Nippon Soda Co., Ltd. Oxadiazole compound and fungicide for agricultural and horticultural use
WO2019020501A1 (en) 2017-07-28 2019-01-31 Basf Se Preparation of substituted 3-aryl-5-trifluoromethyl-1,2,4-oxadiazoles
WO2019150219A2 (en) 2018-01-30 2019-08-08 Pi Industries Ltd. Novel oxadiazoles
US11286242B2 (en) 2018-01-30 2022-03-29 Pi Industries Ltd. Oxadiazoles for use in controlling phytopathogenic fungi
WO2019171234A1 (en) 2018-03-09 2019-09-12 Pi Industries Ltd. Heterocyclic compounds as fungicides
WO2019224160A1 (en) 2018-05-25 2019-11-28 Syngenta Participations Ag Microbiocidal picolinamide derivatives
WO2020025807A1 (en) 2018-08-03 2020-02-06 Syngenta Crop Protection Ag Microbiocidal 1,2,5-oxadiazol-3(2h)-one derivatives
WO2020053364A1 (en) 2018-09-13 2020-03-19 Syngenta Participations Ag Pesticidally active azole-amide compounds
WO2020053365A2 (en) 2018-09-13 2020-03-19 Syngenta Participations Ag Pesticidally active azole-amide compounds
WO2020070610A1 (en) 2018-10-01 2020-04-09 Pi Industries Ltd. Novel oxadiazoles
WO2020070611A1 (en) 2018-10-01 2020-04-09 Pi Industries Ltd Oxadiazoles as fungicides
WO2020079111A1 (en) 2018-10-18 2020-04-23 Syngenta Crop Protection Ag Microbiocidal compounds
WO2020079198A1 (en) 2018-10-19 2020-04-23 Syngenta Participations Ag Pesticidally active azole-amide compounds
WO2020094363A1 (en) 2018-11-05 2020-05-14 Syngenta Participations Ag Pesticidally active azole-amide compounds
WO2020109511A1 (en) 2018-11-30 2020-06-04 Syngenta Crop Protection Ag Microbiocidal 2-acylamino-thiazole-4-carboxamide derivatives
WO2020109509A1 (en) 2018-11-30 2020-06-04 Syngenta Participations Ag Microbiocidal thiazole derivatives
WO2020165403A1 (en) 2019-02-15 2020-08-20 Syngenta Crop Protection Ag Phenyl substituted thiazole derivatives as microbiocidal compounds
WO2020169526A1 (en) 2019-02-18 2020-08-27 Syngenta Crop Protection Ag Pesticidally-active cyanamide heterocyclic compounds
WO2020169445A1 (en) 2019-02-18 2020-08-27 Syngenta Crop Protection Ag Pesticidally active azole-amide compounds
WO2020182649A1 (en) 2019-03-08 2020-09-17 Syngenta Crop Protection Ag Pesticidally active azole-amide compounds
WO2020188027A1 (en) 2019-03-20 2020-09-24 Syngenta Crop Protection Ag Pesticidally active azole amide compounds
WO2020188014A1 (en) 2019-03-20 2020-09-24 Syngenta Crop Protection Ag Pesticidally active azole amide compounds
WO2020193341A1 (en) 2019-03-22 2020-10-01 Syngenta Crop Protection Ag N-[1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-2-cyclopropyl-6-(trifluoromethyl)pyridine-4-carboxamide derivatives and related compounds as insecticides
WO2020193387A1 (en) 2019-03-22 2020-10-01 Syngenta Crop Protection Ag Fungicidal compounds
WO2020193618A1 (en) 2019-03-27 2020-10-01 Syngenta Crop Protection Ag Microbiocidal thiazole derivatives
WO2020201079A1 (en) 2019-03-29 2020-10-08 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2020201398A1 (en) 2019-04-05 2020-10-08 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2020208095A1 (en) 2019-04-10 2020-10-15 Syngenta Crop Protection Ag Microbiocidal picolinamide derivatives
WO2020208096A1 (en) 2019-04-10 2020-10-15 Syngenta Crop Protection Ag Fungicidal compositions
WO2020208036A1 (en) 2019-04-11 2020-10-15 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2020239853A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2020239855A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2020239854A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2020239856A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2020254530A1 (en) 2019-06-18 2020-12-24 Syngenta Crop Protection Ag 7-sulfonyl-n-(1,3,4-thiadiazol-2-yl)-quinoxaline-6-carboxamide derivatives and the respective -benzimidazole-5-, -imidazo[4,5-b]pyridine-5-, -3h-furo[3,2b]pyridine-5-, -quinoline-2-, and -naphthalene-2-carboxamide derivatives as pesticides
WO2021004968A1 (en) 2019-07-05 2021-01-14 Syngenta Crop Protection Ag Microbiocidal picolinamide derivatives
WO2021009026A1 (en) 2019-07-12 2021-01-21 Syngenta Crop Protection Ag Methyl 2-[(4-methoxyimino-tetralin-6-yl]prop-2-enoate derivatives, chromane, isochromane, 6,7,8,9-tetrahydrobenzo[7]annulene, 1h-isobenzofurane and indane analogues thereof, and similar compounds, as agrochemical fungicides
WO2021033133A1 (en) 2019-08-19 2021-02-25 Pi Industries Ltd. Novel oxadiazole compounds containing 5- membered heteroaromatic ring for controlling or preventing phytopathogenic fungi
WO2021032634A1 (en) 2019-08-21 2021-02-25 Syngenta Participations Ag Apparatus and method for reducing dust development in precision drill sowing
WO2021032630A1 (en) 2019-08-21 2021-02-25 Syngenta Participations Ag Sowing device and method for treating seeds during planting
WO2021032631A1 (en) 2019-08-21 2021-02-25 Syngenta Participations Ag Precision treatment and sowing or planting method and device
WO2021032632A1 (en) 2019-08-21 2021-02-25 Syngenta Participations Ag Apparatus and method for converting existing sowing equipment
WO2021032633A1 (en) 2019-08-21 2021-02-25 Syngenta Participations Ag High precision greenhouse seed and seedling treatment
WO2021037614A1 (en) 2019-08-23 2021-03-04 Syngenta Crop Protection Ag Pesticidally active pyrazine-amide compounds
WO2021043616A1 (en) 2019-09-02 2021-03-11 Syngenta Crop Protection Ag Strigolactone derivatives as plant growth regulator compounds
WO2021053110A1 (en) 2019-09-20 2021-03-25 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur and sulfoximine containing substituents
WO2021053161A1 (en) 2019-09-20 2021-03-25 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2021083936A1 (en) 2019-11-01 2021-05-06 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2021100745A1 (en) * 2019-11-21 2021-05-27 日本曹達株式会社 Oxadiazole compound and germicide for agricultural and horticultural use
WO2021110891A1 (en) 2019-12-04 2021-06-10 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic amino compounds
WO2021122645A1 (en) 2019-12-20 2021-06-24 Syngenta Crop Protection Ag Pesticidally active azole-amide compounds
WO2021136722A1 (en) 2019-12-31 2021-07-08 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021140122A1 (en) 2020-01-06 2021-07-15 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021144354A1 (en) 2020-01-15 2021-07-22 Syngenta Crop Protection Ag Pesticidally-active bicyclic heteroaromatic compounds
WO2021148639A1 (en) 2020-01-24 2021-07-29 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2021151926A1 (en) 2020-01-30 2021-08-05 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic amino compounds
WO2021160680A1 (en) 2020-02-11 2021-08-19 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2021170881A1 (en) 2020-02-27 2021-09-02 Syngenta Crop Protection Ag Pesticidally active diazine-bisamide compounds
WO2021175822A1 (en) 2020-03-02 2021-09-10 Syngenta Crop Protection Ag Pesticidally amidine-substituted benzoic acid amide compounds
WO2021176007A1 (en) 2020-03-05 2021-09-10 Syngenta Crop Protection Ag Fungicidal compositions
WO2021176057A1 (en) 2020-03-05 2021-09-10 Syngenta Crop Protection Ag Fungicidal compositions
WO2021180975A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021180976A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola, cercospora sojina and/or cercospora kikuchii
WO2021180974A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021180598A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021180592A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021180596A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021204857A1 (en) 2020-04-08 2021-10-14 Syngenta Crop Protection Ag Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives
WO2021204822A1 (en) 2020-04-08 2021-10-14 Syngenta Crop Protection Ag Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives
WO2021204855A1 (en) 2020-04-08 2021-10-14 Syngenta Crop Protection Ag Microbiocidal quinoline dihydropyrrolopyrazine derivatives
WO2021213929A1 (en) 2020-04-20 2021-10-28 Syngenta Crop Protection Ag Pesticidally active substituted 1,3-dihydro-2h-imidazo[4,5-c]pyridin-2-one derivatives with sulfur containing substituents
WO2021219775A1 (en) 2020-04-30 2021-11-04 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021219778A1 (en) 2020-04-30 2021-11-04 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021219810A1 (en) 2020-04-30 2021-11-04 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021219780A1 (en) 2020-05-01 2021-11-04 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021224102A1 (en) 2020-05-05 2021-11-11 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021224409A1 (en) 2020-05-06 2021-11-11 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021244952A1 (en) 2020-06-03 2021-12-09 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2021244950A1 (en) 2020-06-03 2021-12-09 Syngenta Crop Protection Ag Fungicidal compositions
WO2021244951A1 (en) 2020-06-03 2021-12-09 Syngenta Crop Protection Ag Fungicidal compositions
WO2021251274A1 (en) 2020-06-08 2021-12-16 日本曹達株式会社 Method for reducing or preventing effect of non-biological stress on plant
WO2022013417A1 (en) 2020-07-17 2022-01-20 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022017975A1 (en) 2020-07-18 2022-01-27 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022043576A2 (en) 2020-08-31 2022-03-03 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022049141A1 (en) 2020-09-01 2022-03-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022049146A1 (en) 2020-09-02 2022-03-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022048988A1 (en) 2020-09-02 2022-03-10 Syngenta Participations Ag Plant growth regulator compounds
WO2022049144A1 (en) 2020-09-02 2022-03-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022053567A1 (en) 2020-09-09 2022-03-17 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022058580A1 (en) 2020-09-21 2022-03-24 Syngenta Crop Protection Ag Microbiocidal compounds
WO2022084346A1 (en) 2020-10-22 2022-04-28 Syngenta Crop Protection Ag Zealactone derivatives as plant growth regulators
WO2022101265A1 (en) 2020-11-13 2022-05-19 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2022117650A1 (en) 2020-12-02 2022-06-09 Syngenta Crop Protection Ag Fungicidal compositions
WO2022117653A1 (en) 2020-12-02 2022-06-09 Syngenta Crop Protection Ag Fungicidal compositions
WO2022157334A1 (en) 2021-01-21 2022-07-28 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022157122A1 (en) 2021-01-22 2022-07-28 Syngenta Crop Protection Ag Method for the control or suppression of phytopathogenic bacteria
WO2022157188A2 (en) 2021-01-23 2022-07-28 Syngenta Crop Protection Ag Pesticidally active heteroaromatic compounds
WO2022207479A1 (en) 2021-03-27 2022-10-06 Syngenta Crop Protection Ag Microbiocidal isonicotinic amide derivatives
WO2022207462A1 (en) 2021-03-30 2022-10-06 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2022207665A1 (en) 2021-03-31 2022-10-06 Syngenta Crop Protection Ag Microbiocidal quinoline/quinoxaline benzothiazine derivatives
WO2022219146A2 (en) 2021-04-16 2022-10-20 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2022223376A1 (en) 2021-04-20 2022-10-27 Syngenta Crop Protection Ag Microbiocidal quinoline/quinoxaline isoquinoline derivatives
WO2022233869A1 (en) 2021-05-04 2022-11-10 Syngenta Crop Protection Ag Use of clethodim for insect control
EP4094579A1 (en) * 2021-05-28 2022-11-30 Basf Se Pesticidal mixtures comprising metyltetraprole
WO2022253645A1 (en) 2021-06-01 2022-12-08 Syngenta Crop Protection Ag Microbiocidal tetrahydroisoquinoline derivatives
WO2022253841A1 (en) 2021-06-02 2022-12-08 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfoximine containing substituents
WO2022258481A1 (en) 2021-06-09 2022-12-15 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2022268648A1 (en) 2021-06-24 2022-12-29 Syngenta Crop Protection Ag 2-[3-[1 [(quinazolin-4-yl)amino]ethyl]pyrazin-2-yl]thiazole-5-carbonitrile derivatives and similar compounds as pesticides
WO2023275116A1 (en) 2021-07-02 2023-01-05 Syngenta Crop Protection Ag Use of fluazifop-p-butyl for insect control
WO2023006634A1 (en) 2021-07-27 2023-02-02 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023006789A1 (en) 2021-07-29 2023-02-02 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2023012044A1 (en) 2021-08-02 2023-02-09 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2023012081A1 (en) 2021-08-05 2023-02-09 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023017016A1 (en) 2021-08-10 2023-02-16 Syngenta Crop Protection Ag Fungicide mixture
WO2023017094A1 (en) 2021-08-10 2023-02-16 Syngenta Crop Protection Ag 2,2-difluoro-5h-[1,3]dioxolo[4,5-f]isoindol-7-one derivatives as pesticides
WO2023021020A1 (en) 2021-08-19 2023-02-23 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023061838A1 (en) 2021-10-14 2023-04-20 Syngenta Crop Protection Ag Imidazo[1,2-a]pyridine derivatives
WO2023072945A1 (en) 2021-10-25 2023-05-04 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023072849A1 (en) 2021-10-27 2023-05-04 Syngenta Crop Protection Ag Pesticidally active pyridazinone compounds
WO2023072785A1 (en) 2021-10-29 2023-05-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2023072784A1 (en) 2021-10-29 2023-05-04 Syngenta Crop Protection Ag Fungicidal compositions comprising fludioxonil
WO2023089049A2 (en) 2021-11-19 2023-05-25 Syngenta Crop Protection Ag Microbiocidal isonicotinic amide derivatives
WO2023094303A1 (en) 2021-11-25 2023-06-01 Syngenta Crop Protection Ag Microbiocidal heterobiaryl amide derivatives
WO2023094304A1 (en) 2021-11-25 2023-06-01 Syngenta Crop Protection Ag Microbiocidal heterobiaryl amide derivatives
WO2023099460A1 (en) 2021-12-02 2023-06-08 Syngenta Crop Protection Ag Fungicidal compositions
WO2023104714A1 (en) 2021-12-10 2023-06-15 Syngenta Crop Protection Ag Pesticidally active pyridazinone compounds
WO2023110710A1 (en) 2021-12-13 2023-06-22 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
EP4197333A1 (en) 2021-12-15 2023-06-21 Syngenta Crop Protection AG Method for controlling diamide resistant pests & compounds therefor
WO2023110869A1 (en) 2021-12-15 2023-06-22 Syngenta Crop Protection Ag Microbiocidal bicycle heterocyclic derivatives
WO2023110871A1 (en) 2021-12-17 2023-06-22 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2023110928A1 (en) 2021-12-17 2023-06-22 Syngenta Crop Protection Ag Fungicidal compositions
WO2023111215A1 (en) 2021-12-17 2023-06-22 Syngenta Crop Protection Ag Microbiocidal pyridine-substituted benzothiazine derivatives
WO2023117625A1 (en) 2021-12-22 2023-06-29 Syngenta Crop Protection Ag Fungicidal compositions
WO2023118011A1 (en) 2021-12-22 2023-06-29 Syngenta Crop Protection Ag Microbiocidal aza-heterobiaryl derivatives
WO2023118434A1 (en) 2021-12-22 2023-06-29 Globachem Nv Pesticidally active amide compounds
WO2023139166A1 (en) 2022-01-19 2023-07-27 Syngenta Crop Protection Ag Methods for controlling plant pathogens
WO2023148206A1 (en) 2022-02-02 2023-08-10 Syngenta Crop Protection Ag Microbiocidal n-amide derivatives
WO2023148368A1 (en) 2022-02-07 2023-08-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023148369A1 (en) 2022-02-07 2023-08-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023166067A1 (en) 2022-03-02 2023-09-07 Syngenta Crop Protection Ag Microbiocidal pyridazinone amide derivatives
WO2023187191A1 (en) 2022-04-01 2023-10-05 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023209238A1 (en) 2022-04-29 2023-11-02 Syngenta Crop Protection Ag Fungicidal compositions
WO2023217989A1 (en) 2022-05-12 2023-11-16 Syngenta Crop Protection Ag Alkoxy heteroaryl- carboxamide or thioamide compounds
WO2023247360A1 (en) 2022-06-21 2023-12-28 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2023247552A1 (en) 2022-06-21 2023-12-28 Syngenta Crop Protection Ag Microbiocidal bicyclic heterocyclic carboxamide derivatives
WO2024008567A1 (en) 2022-07-07 2024-01-11 Syngenta Crop Protection Ag Precision application devices and compositions
WO2024018016A1 (en) 2022-07-21 2024-01-25 Syngenta Crop Protection Ag Crystalline forms of 1,2,4-oxadiazole fungicides
WO2024017788A1 (en) 2022-07-22 2024-01-25 Syngenta Crop Protection Ag Solid form of a heterocyclic amide derivative
WO2024022910A1 (en) 2022-07-26 2024-02-01 Syngenta Crop Protection Ag 1-[1-[2-(pyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-3-[2,4-dichloro-5-phenyl]urea derivatives and similar compounds as pesticides
WO2024033374A1 (en) 2022-08-11 2024-02-15 Syngenta Crop Protection Ag Novel arylcarboxamide or arylthioamide compounds
WO2024038053A1 (en) 2022-08-16 2024-02-22 Syngenta Crop Protection Ag New use of pydiflumetofen
WO2024056732A1 (en) 2022-09-16 2024-03-21 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2024068838A1 (en) 2022-09-28 2024-04-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2024068656A1 (en) 2022-09-28 2024-04-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2024068655A1 (en) 2022-09-28 2024-04-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2024068950A1 (en) 2022-09-30 2024-04-04 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2024068947A1 (en) 2022-09-30 2024-04-04 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives

Also Published As

Publication number Publication date
JP2019506364A (en) 2019-03-07
CL2018001469A1 (en) 2018-07-20
CO2018005793A2 (en) 2018-07-10
CN108289448B (en) 2021-10-22
UY36999A (en) 2017-06-30
BR112018011053A2 (en) 2018-11-21
IL259695A (en) 2018-07-31
MX2018006474A (en) 2018-08-01
US10640497B2 (en) 2020-05-05
CN108289448A (en) 2018-07-17
US20180362515A1 (en) 2018-12-20
ZA201802969B (en) 2019-02-27
JP6930972B2 (en) 2021-09-01
IL259695B (en) 2021-10-31

Similar Documents

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

Legal Events

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

Ref document number: 16802115

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: MX/A/2018/006474

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 259695

Country of ref document: IL

WWE Wipo information: entry into national phase

Ref document number: 2018528660

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112018011053

Country of ref document: BR

WWE Wipo information: entry into national phase

Ref document number: 2016802115

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2016802115

Country of ref document: EP

Effective date: 20180702

ENP Entry into the national phase

Ref document number: 112018011053

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20180530