WO2004035589A1 - Heterocyclocarboxamide derivatives - Google Patents

Heterocyclocarboxamide derivatives Download PDF

Info

Publication number
WO2004035589A1
WO2004035589A1 PCT/EP2003/011388 EP0311388W WO2004035589A1 WO 2004035589 A1 WO2004035589 A1 WO 2004035589A1 EP 0311388 W EP0311388 W EP 0311388W WO 2004035589 A1 WO2004035589 A1 WO 2004035589A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogen
formula
alkyl
alkoxy
compound
Prior art date
Application number
PCT/EP2003/011388
Other languages
French (fr)
Inventor
Josef Ehrenfreund
Hans Tobler
Harald Walter
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=9946176&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2004035589(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority to MXPA05003899A priority Critical patent/MXPA05003899A/en
Priority to UAA200504639A priority patent/UA81784C2/en
Priority to AT03772217T priority patent/ATE460418T1/en
Priority to EP03772217A priority patent/EP1556385B1/en
Priority to YU20050297A priority patent/RS51937B/en
Priority to EA200500574A priority patent/EA010264B1/en
Priority to SI200331806T priority patent/SI1556385T1/en
Priority to NZ539376A priority patent/NZ539376A/en
Priority to AU2003280376A priority patent/AU2003280376B2/en
Priority to US10/530,737 priority patent/US7598395B2/en
Priority to MEP-316/08A priority patent/MEP31608A/en
Application filed by Syngenta Participations Ag filed Critical Syngenta Participations Ag
Priority to JP2004544232A priority patent/JP4607591B2/en
Priority to DE60331670T priority patent/DE60331670D1/en
Priority to MEP-2008-316A priority patent/ME00223B/en
Priority to BRPI0314875-0A priority patent/BR0314875B1/en
Priority to DK03772217.0T priority patent/DK1556385T3/en
Priority to CA2498851A priority patent/CA2498851C/en
Publication of WO2004035589A1 publication Critical patent/WO2004035589A1/en
Priority to IL167290A priority patent/IL167290A/en
Priority to EGNA2005000128 priority patent/EG24050A/en
Priority to TNP2005000112A priority patent/TNSN05112A1/en
Priority to NO20052201A priority patent/NO331404B1/en
Priority to HRP20050441AA priority patent/HRP20050441B1/en
Priority to HK06104366.2A priority patent/HK1082254A1/en
Priority to IL190341A priority patent/IL190341A/en
Priority to US12/549,478 priority patent/US7994093B2/en
Priority to FR18C1024C priority patent/FR18C1024I2/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D213/00Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81Amides; Imides
    • C07D213/82Amides; Imides in position 3
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/32Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms six-membered rings
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/561,2-Diazoles; Hydrogenated 1,2-diazoles
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72Biocides, 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
    • A01N43/74Biocides, 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 one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/761,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72Biocides, 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
    • A01N43/74Biocides, 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 one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/781,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04Antibacterial agents
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D207/00Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D213/00Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D231/00Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D263/00Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D277/00Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/56Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D327/00Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/02Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
    • C07D327/06Six-membered rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D487/00Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/08Bridged systems
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D493/00Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/08Bridged systems
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D495/00Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/08Bridged systems
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00Systems containing at least three condensed rings
    • C07C2603/56Ring systems containing bridged rings
    • C07C2603/58Ring systems containing bridged rings containing three rings
    • C07C2603/60Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
    • C07C2603/66Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings

Definitions

  • the present invention relates to novel tricyclic amine derivatives which have microbiocidal activity, in particular fiingicidal activity.
  • the invention also relates to the preparation of these compounds, to novel intermediates used in the preparation of these compounds, to agrochemical compositions which comprise at least one of the novel compounds as active ingredient, to the preparation of the compositions mentioned and to the use of the active ingredients or compositions in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.
  • the present invention provides a compound of formula (I):
  • Het is a 5- or 6-membered heterocyclic ring containing one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, provided that the ring is not 1,2,3-triazole, the ring being substituted by groups R 8 , R 9 and R 10 ;
  • X is a single or double bond;
  • Y is O, S, N(R ⁇ ) or (CR 12 R 13 )(CR I4 R 15 ) m (CR 16 R 17 ) n ;
  • m is 0 or 1;
  • n is 0 or 1;
  • R 2 and R 3 are each, independently, hydrogen, halogen, C alkyl, C ⁇ - alkoxy or C M haloal
  • R 18 , R 19 and R 20 are each, independently, hydrogen, halogen, C M alkyl, C M haloalkyl or C alkoxy(C ⁇ . 4 )alkylene; and R 21 is hydrogen, - 6 alkyl, Cj. 6 haloalkyl, CM alkoxy(C ⁇ -4 )alkylene, CM alkyl-S-(CM)alkylene, C alkoxy or aryl.
  • Halogen is fluoro, chloro, bromo or iodo; preferably fluoro, chloro or bromo.
  • Each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, wo-propyl, sec-butyl, wo-butyl, tert-butyl, ne ⁇ -pentyl, n-heptyl, 1,3-dimethylbutyl, 1,3-dimethylpentyl, l-methyl-3-ethyl-butyl or 1,3,3-trimethylbutyl.
  • each alkylene moiety is a straight or branched chain.
  • Haloalkyl moieties are alkyl moieties which are substituted by one or more of the same or different halogen atoms and are, for example, CF 3 , CF 2 C1, CHF 2 , CH 2 F, CC1 3 , CF 3 CH 2 , CHF 2 CH 2 , CH 2 FCH 2 , CH 3 CHF or CH 3 CF 2 .
  • Alkenyl and alkynyl moieties can be in the form of straight or branched chains.
  • Each alkenyl moiety may be of either the (E)- or ⁇ -configuration.
  • a 3-5 membered carbocyclic ring includes a spiro-three or five membered ring.
  • Aryl includes phenyl, naphthyl, anthracyl, fluorenyl and indanyl but is preferably phenyl.
  • Alkylidene moieties may be in the form of straight or branched chains.
  • Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • Cycloalkenyl includes cyclobutenyl, cyclopentenyl, cyclohexenyl and cycloheptenyl.
  • R 11 is hydrogen, C M alkyl, benzyl (in which the phenyl group is optionally substituted with up to three substituents, each independently selected from halogen, CM alkyl, C M haloalkyl and CM alkoxy), formyl, C(O)C alkyl or C M alkoxy(C M )alkylene.
  • R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are each, independently, hydrogen, C M alkyl or C M alkoxy.
  • Het is preferably pyrrolyl, pyrazolyl, thiazolyl, oxazolyl, pyridinyl, pyrimidyl, pyridazinyl, 2,3-dihydro-[l,4]oxathiine-6-yl, oxazinyl, thiazinyl or triazinyl.
  • Het is more preferably pyrrolyl, pyrazolyl, thiazolyl, oxazolyl, pyridinyl or 2,3-dibydro-[l,4]oxathiine-yl.
  • Het is even more preferably pyrrolyl, pyrazolyl, thiazolyl or pyridinyl. Het is most preferably pyrrolyl or pyrazolyl.
  • X is a single bond.
  • Y is O, S, N(R n ), CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 , C(CH 3 ) 2 , CH(CH 3 ), CH(C 2 H 5 ), C(CH 3 )(C 2 H 5 ), CH(OCH 3 ) or C(OCH 3 ) 2 ; more preferably N(R"), O, S, CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 , C(CH 3 ) 2 , CH(CH 3 ) or CH(C 2 H 5 ) ⁇ even more preferably N(R n ), O, S, CH 2 or CH 2 CH 2 ; and still more preferably O, CH 2 or N(R n ).
  • Y is O, N(R ⁇ ) or (CR 12 R 13 )(CR 14 R 15 ) m (CR l6 R 17 ) ⁇ . More preferably Y is O or (CR l2 R 13 )(CR 14 R ,5 ) m (CR l6 R 17 ) n . Even more preferably Y is (CR l2 R 13 )(CR 14 R 15 ) ra (CR 16 R 17 ) n . Still more preferably Y is (CR 12 R 13 ). Preferably n is 0.
  • R 2 is hydrogen, halogen or C M alkyl.
  • R 2 is hydrogen or halogen. Most preferably R 2 is hydrogen.
  • R 3 is hydrogen or methyl. More preferably R 3 is hydrogen.
  • R 4 is hydrogen, C M alkyl, halogen, C haloalkyl, C M alkoxy, C(O)CH 3 or C(O)OCH 3 .
  • R 4 is hydrogen, C ⁇ . 2 alkyl, halogen, CF 3 , methoxy, C(O)CH 3 or C(O)OCH 3 .
  • R 4 is hydrogen, methyl, chlorine, CF 3 or methoxy. Most preferably R 4 is hydrogen or methyl.
  • R 5 is hydrogen, C M alkyl, halogen, C haloalkyl, CM alkoxy, C(O)CH 3 or C(O)OCH 3 .
  • R 5 is hydrogen, C 1 - 2 alkyl, chlorine, CF 3 , methoxy, C(O)CH 3 or C(O)OCH 3 . Most preferably R 5 is hydrogen or methyl.
  • R 6 is hydrogen, C M alkyl, C alkoxy or C(O)CH 3 . More preferably R 6 is hydrogen, methyl, methoxy or C(O)CH 3 . Most preferably R 6 is hydrogen or methyl.
  • R 7 is hydrogen, C M alkyl, C M alkoxy or C(O)CH 3 . More preferably R 7 is hydrogen, methyl, methoxy or C(O)CH 3 .
  • R 7 is hydrogen or methyl.
  • R 8 is hydrogen, halogen, C M alkyl, C M haloalkyl or methoxymethylene. More preferably R 8 is hydrogen, chloro, fluoro, bromo, C1-2 alkyl, CF 3 , CF 2 C1, CHF 2 , CH 2 F or methoxymethylene. Even more preferably R 8 is hydrogen, chloro, fluoro, C ⁇ - 2 alkyl, CF 3 , CF 2 C1, CHF 2 ,
  • R 8 is hydrogen, chloro, fluoro, methyl, CF 3 , CHF 2 or CH 2 F.
  • R 9 is hydrogen, halogen, C alkyl or C haloalkyl or methoxymethylene.
  • R 9 is hydrogen, chloro, fluoro, bromo, C ⁇ - 2 alkyl, CF 3 , CF 2 C1, CHF 2 , CH 2 F or methoxymethylene. Even more preferably R 9 is hydrogen, chloro, fluoro, C ⁇ - 2 alkyl, CF 3 , CF 2 C1, CHF 2 ,
  • R 9 is hydrogen, chloro, fluoro, methyl, CF 3 , CHF 2 or CH 2 F.
  • R 10 is hydrogen, halogen, C M alkyl, C M aloalkyl or methoxymethylene. More preferably R 10 is hydrogen, chloro, fluoro, bromo, Cj. 2 alkyl, CF 3 , CF 2 C1, CHF 2 , CH 2 F or methoxymethylene.
  • R 10 is hydrogen, chloro, fluoro, C ⁇ . 2 alkyl, CF 3 , CF 2 C1, CHF 2 , CH 2 F or methoxymethylene.
  • R 10 is hydrogen, chloro, fluoro, methyl, CF , CHF 2 or CH 2 F.
  • R 11 is hydrogen, C M alkyl, benzyl, formyl, C(O)CH 3 or C(O)OC(CH 3 ) 3 ; more preferably hydrogen or C ⁇ - 2 alkyl.
  • R 11 is C alkyl, formyl, C(O)CH 3 or C(O)OC w alkyl (optionaUy substituted by halogen, CN or C alkoxy). More preferably R 11 is C(O)OC ⁇ - 4 alkyl.
  • R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are each, independently, hydrogen, d. 2 alkyl or methoxy.
  • R 12 and R 13 are, independently, H, CH 3 , C 2 H 5 , n-C 3 H 7). /-C 3 H 7 , «-C H 9 , ⁇ , ec-C 4 H 9 , /-C 4 H 9 , CH(C 2 H 5 ) 2 , CH 2 -cyclopropyl or cyclopentyl; or R 12 and R 13 together with the carbon atom to which they are attached form a 3-membered or 5-membered carbocyclic ring.
  • R 14 is H or CH 3 .
  • R 15 is H or CH 3 .
  • R 16 is H or CH 3 .
  • R 17 is H or CH 3 .
  • R 18 is hydrogen, chloro, bromo, methyl or methoxy.
  • R 18 is hydrogen, chloro or methyl.
  • R 18 is hydrogen.
  • R 19 is hydrogen, chloro, bromo, methyl or methoxy.
  • R 19 is hydrogen, chloro or methyl.
  • R 19 is hydrogen.
  • R 20 is hydrogen, chloro, bromo, methyl or methoxy.
  • R 20 is hydrogen, chloro or methyl. Most preferably R 20 is hydrogen.
  • R 21 is hydrogen, methyl, OC(CH 3 ) 3 or CH 3 OCH 2 .
  • the present invention provides a compound of formula (C) where Y is O or S; and R 4 , R 5 , R 6 and R 7 are each C(O)OCH 3 ; or Y is N(R' ') or (CR 12 R 13 )(CR l4 R 15 ) m (CR l0 R ,7 ) n ; R 4 , R 5 , R 6 , R 7 , R 14 , R 15 , R 16 , R 17 , m and n are each as defined above for a compound of formula (I); R 11 is benzyl (in which the phenyl group is optionally substituted with up to three substituents, each independently selected from halogen, C M alkyl, C M haloalkyl and C M alkoxy); and R 12 and R 13 together with the carbon atom to which they are attached form a 3-5 membered carbocyclic ring (optionally substituted by up to three methyl groups and containing 1 or 2 hetero
  • the present invention provides a compound of formula (D) where Y is O or S; and R 4 , R 5 , R 6 and R 7 are each C(O)OCH 3 ; or Y is N(R") or (CR 12 R 13 )(CR 14 R 15 ) m (CR 16 R 17 ) n ; R 4 , R 5 , R 6 , R 7 , R 14 , R 15 , R 16 , R 17 , m and n are each as defined above for a compound of formula (I); R u is benzyl (in which the phenyl group is optionally substituted with up to three substituents, each independently selected from halogen, C alkyl, C M haloalkyl and C M alkoxy) ; and R 12 and R 13 together with the carbon atom to which they are attached form a 3-5 membered carbocyclic ring (optionally substituted by up to three methyl groups and containing 1 or 2 heteroatoms each independently selected from O
  • the compounds of formula (I), (C) and (D) may exist as different geometric or optical isomers or in different tautomeric forms.
  • This invention covers, for each formula, all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.
  • Table 1 provides 94 compounds of formula (C) wherein Y, R 4 , R 5 , R 6 and R 7 are as defined in Table 1.
  • Table 2 provides 111 compounds of formula (D) wherein Y, R 4 , R 5 , R 6 and R 7 are defined in Table 2.
  • Table Z represents Table 3 [when Z is 3], Table 4 [when Z is 4], Table 5 [when Z is 5], Table 6 [when Z is 6] , Table 7 [when Z is 7], Table 8 [when Z is 8], Table 9 [when Z is 9], Table 10 [when Z is 10], Table 11 [when Z is 11], Table 12 [when Z is 12] , Table 13 [when Z is 13], Table 14 [when Z is 14], Table 15 [when Z is 15], Table 16 [when Z is 16], Table 17 [when Z is 17], Table 18 [when Z is 18], Table 19 [when Z is 19], Table 20 [when Z is 20], Table 21 [when Z is 21], Table 22 [when Z is 22], Table 23 [when Z is 23], Table 24 [when Z is 24], Table 25 [when Z is 25], Table 26 [when Z is 26], Table 27 [when Z is 27], Table 28 [when Z is 28] and represents Table 29 [when Z s 29].
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 3.
  • Table 4 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 4.
  • Table 5 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 5.
  • Table 6 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 6.
  • Table 7 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 7.
  • Table 8 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 8.
  • Table 9 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 10.
  • Table 11 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 11.
  • Table 12 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 12.
  • Table 13 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 13.
  • Table 14 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 14.
  • Table 15 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 15.
  • Table 16 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 16.
  • Table 17 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 17.
  • Table 18 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 18.
  • Table 19 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 19.
  • Table 20 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 20.
  • Table 21 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 21.
  • Table 22 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 22.
  • Table 23 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 23.
  • Table 24 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 24.
  • Table 25 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 25.
  • Table 26 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R l , R 4 , R 5 , R 6 and R 7 are as defined in Table 26.
  • Table 27 provides 235 compounds of formula (I) where Het is
  • R 2 and R , 3 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 27.
  • Table 28 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 28.
  • Table 29 provides 235 compounds of formula (I) where Het is
  • R 2 and R 3 are both hydrogen; and X, Y, R 1 , R 4 , R 5 , R 6 and R 7 are as defined in Table 29.
  • Table 30 shows selected melting point and selected NMR data, all with CDC1 3 as the solvent (unless otherwise stated; if a mixture of solvents is present, this is indicated as, for example, [CDC1 3 / d 6 -DMSO]), (no attempt is made to list all characterising data in all cases) for compounds of Tables 1 to 29.
  • a compound of formula (I) [where R 1 is hydrogen; and Het, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X and Y are as defined above for a compound of formula (I)] may be synthesized by reacting a compound of (II) [where Het is as defined above for a compound of formula (I) and R' is C,. 5 alkyl] with an aniline of formula (III) [where R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X and Y are as defined above for a compound of formula (I)] in the presence of NaN(TMS) 2 at -10°C to ambient temperature, preferably in dry THF, as described by J. Wang et al. Synlett, 2001, 1485. Scheme 2
  • a compound of formula (I) [where R 1 is hydrogen; and Het, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X and Y are as defined above for a compound of formula (I)] may be prepared by reacting a compound of formula (II') [where Het is as defined above for a compound of formula (I)] with an aniline of formula (III) [where R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X and Y are as defined above for a compound of formula (I)] in the presence of an activating agent [such as BOP-C1] and two equivalents of a base [such as triethylamine] or by reacting a compound of formula (II") [where Het is as defined above for a compound of formula (I); and Q is Cl, F or Br] which is obtained from a compound of formula (IF) by treatment with a halogenating agent such as thiony
  • OCOR* in the presence of a base [for example NaH, NEt 3 , NaHCO 3 or K 2 CO 3 ] in an appropriate solvent [such as ethyl acetate] or in a biphasic mixture [such as dichloromethane /water mixture], at -10 to 30°C.
  • a base for example NaH, NEt 3 , NaHCO 3 or K 2 CO 3
  • an appropriate solvent such as ethyl acetate
  • a biphasic mixture such as dichloromethane /water mixture
  • Ortbo-substituted aminobenzonorbonenes may be accomplished through Diels-Alder addition of an in situ generated benzyne [for example starting from a 6-nitroanthranilic acid of formula (A), as described by L.Paquette et al, J. Amer. Chem. Soc. 99, 3734 (1977) or from other suitable precursers (see H. Pellissier et al.
  • Suitable aprotic solvents for this step include ethyl acetate, dichloromethane, acetone, THF and dimethoxyethane. Reaction temperatures range from room temperature to 100°C, preferably 40-80°C. Subsequent selective reduction of the nitro-group in a compound of formula (B) to give an amino-benzonorbornadiene of formula (C) requires mild conditions [for example, either metallic zinc in the presence of ammonium chloride, or aluminium amalgam].
  • a compound of formula (C) may also be obtained from a compound of formula (B) by catalytic hydrogen reduction with a modified 5% Pt/C catalyst at elevated pressure ( ⁇ 10bar) and elevated temperature ( ⁇ 100°C) in toluene- water.
  • Catalytic reduction under standard conditions for example 5% Pd C or 5% Ra Ni or 5% Rh/C
  • a solvent such as methanol, ethanol, THF or ethyl acetate
  • novel compounds of formula (I) have, for practical purposes, a very advantageous spectrum of activities for protecting plants against diseases that are caused by fungi as well as by bacteria and viruses.
  • the compounds of formula (I) can be used in the agricultural sector and related fields of use as active ingredients for controlling plant pests.
  • 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 are 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.
  • compounds of formula (I) as dressing agents for the treatment of plant propagation material, in particular of seeds (fruit, tubers, grains) and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
  • the compounds according to present invention may 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, etc.
  • the compounds of formula (I) are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Hekninthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e.g. Nenturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes classes (e.g. Phytophthora, Pythium, Plasmopara).
  • Fungi imperfecti e.g. Botrytis, Pyricularia, Hekninthosporium, Fusarium, Septoria, Cercospora and Alternaria
  • Basidiomycetes e.g. Rhizoctonia, Hemileia, Puccini
  • novel compounds of formula I are effective against phytopathogenic bacteria and viruses (e.g. against Xanthomonas spp, Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus).
  • target crops to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamomum, camphor) or plants such as tobacco
  • the compounds of formula (I) are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they are conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, 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.
  • 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 WO97/33890.
  • the compounds of formula (I) are normally used in the form of 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 can also be 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) can be mixed with other fungicides, resulting in some cases in unexpected synergistic activities.
  • Mixing components which are particularly preferred are azoles, such as azaconazole, BAY 14120, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibencon- azole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole; pyrimidinyl carb
  • a preferred method of applying 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.
  • the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, for example 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 that is, a composition containing the compound of formula (I)] and, if desired, a solid or liquid adjuvant, is 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).
  • the agrochemical formulations will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the compound of formula I, 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant.
  • Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from lOg to 1kg a.i./ha, most preferably from 20g to 600g a.i./ha.
  • convenient dosages are from lOmg to lg of active substance per kg of seeds.
  • the end user will normally use dilute formulations.
  • EXAMPLE 3 This Example illustrates the preparation of Compound No. 2.16.
  • a solution of 5-nitrobenzonorbornadiene (L.A. Paquette et al., J. Amer. Chem. Soc. 99, 3734 (1977)) (2.52g; 13.46mmol) in methanol (100ml) was hydrogenated in the presence of 5% Pd/C (0.5g) at ambient temperature.
  • H 2 -uptake was 1.141itres (95%) after 11 minutes.
  • the solution was filtered from the catalyst and evaporated to give pure product (1.86g; 87% ) as a yellow oil, which solidified on standing at room temperature (m.p. 63-64°C).
  • This Example illustrates the preparation of Compound No.3.024.
  • a suspension of NaH (0.107g; 60% oil dispersion, ⁇ 2.7mmol) in DMF (5ml) was reacted with a solution of 1 -methyl-4-trifluoromethyl- 1 H-pyrrole-3-carboxylic acid( 1 ,8- dimethyl-1 l-oxa-tricyclo[6.2.1.0*2,7*]undeca-2,4,6-trien-3-yl)-amide (Compound No. 3.023; see preparation above) (0.65g; 1.784mmol) in 5ml DMF at 10-15°C for 30minutes.
  • Example B-l Action against Puccinia recondita / wheat (Brownrust on wheat)
  • Example B-2 Action against Podosphaera leucotricha / apple (Powdery mildew on apple)
  • Example B-3 Action against Nenturia inaequalis / apple ( " Scab on apple)
  • Example B-5 Action against Botrytis cinerea / grape (Botrytis on grapes)
  • Example B-6 Action against Botrytis cinerea / tomato (Botrytis on tomatoes)
  • Example B-7 Action against Septoria nodorum / wheat (Septoria leaf spot on wheat .
  • 1 week old wheat plants cv. Arina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber.
  • the wheat plants are inoculated by spraying a spore suspension (5xl0 5 conidia/ml) on the test plants.
  • a spore suspension 5xl0 5 conidia/ml
  • the plants After an incubation period of 1 day at 20°C and 95%r.h. the plants are kept for 10 days at 20°C and 60%r.h. in a greenhouse.
  • the disease incidence is assessed 11 days after inoculation.
  • Example B-8 Action against Helminthosporium teres / barley (Net blotch on barley)
  • Example B-9 Action against Alternaria solani / tomato (Early blight on tomatoes)
  • Example B-10 Action against Uncinula necator / grape (Powdery mildew on grapes) 5week old grape seedlings cv. Gutedel are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the grape plants are inoculated by shaking plants infected with grape powdery mildew above the test plants. After an incubation period of 7days at 26°C and 60%r.h. under a light regime of 14/10hours (light/dark) the disease incidence is assessed.
  • Example B-l 1 Systemic Action against Erysiphe graminis / barley (Powdery mildew on barley) (Pouch test)
  • the formulated test compound (0.002% active ingredient) is applied into a pouch which was previously equipped with a filter paper. After the application barley seeds (cv.Express) are sown into the upper fault of the filter paper. The prepared pouches are then incubated at 23°C/18°C (day/night) and 80%r.h. One week after sowing barley plants were inoculated by shaking powdery mildew infected plants above the test plants.
  • Example B-l 2 Action against Fusarium culmorum / wheat (Fusarium head blight on wheat) (Pouch test)
  • a conidia suspension of F. culmorum (7xl0 5 conidia/ml) is mixed with the formulated test compound (0.002% active ingredient).
  • the mixture is applied into a pouch which was previously equipped with a filter paper. After the application wheat seeds (cv.Orestis) are sown into the upper fault of the filter paper.
  • the prepared pouches are then incubated for 1 ldays at ca.10-18° C and 100%r.h. with a daily light period of
  • the evaluation is made by assessing the degree of disease occurrence in the form of brown lesions on the roots.
  • Example B-13 Action Gaeumannomyces graminis / wheat (Take- all on wheat) (pouch test) A defined amount of mycelium of G. graminis is mixed with water. The formulated test compound (0.002% active ingredient) is added to the mycelium suspension. The mixture is applied into a pouch which was previously equipped with a filter paper. After the application wheat seeds (cv.Orestis) are sown into the upper fault of the filter paper.
  • the prepared pouches are then incubated for 14days at 18°C/16°C (day/night) and 80%r.h. with a daily light period of 14hours.
  • the evaluation is made by assessing the degree of root browning.
  • Compounds 15.048, 20.048, 21.048, 15.028 and 15.052 each show good activity in this test ( ⁇ 50% disease incidence).
  • Example B-14 Action against Puccinia recondita / wheat (Brownrust on wheat) (Pouch test)
  • Formulated test compound (0.002% active ingredient) is applied into a pouch which was previously equipped with a filter paper. After the application wheat seeds (cv.Arina) are sown into the upper fault of the filter paper. The prepared pouches are then incubated at 23°C/18°C (day/night) and 80%r.h.
  • the wheat plants were inoculated by spraying a spore suspension (lxl0 5 uredospores/ml) on the test plants. After an incubation period of lday at 23°C and 95%r.h. the plants were kept for 9days at 20°C/18°C (day/night) and 80%r.h .
  • the disease incidence was assessed lOdays after inoculation.
  • the efficacy of each test compound is used as an indicator for systemic activity.
  • Example B-15 Action against Rhizoctonia solani / rice (Sheath blight on rice) (Pouch test)
  • a defined amount of mycelium of R. solani is mixed with water.
  • the formulated test compound (0.002% active ingredient) is added to the mycelium suspension.
  • the mixture is applied into a pouch which was previously equipped with a filter paper.
  • rice seeds cv.Koshihikari
  • the prepared pouches are then incubated for lOdays at 23°C/21°C (day/night) and 100%r.h. with a daily light period of 14hours.
  • the evaluation is made by assessing the degree of disease occurrence in the form of brown lesions on the roots.
  • Example B-16 Action against Septoria nodorum / wheat (Septoria leaf spot on wheat) .Pouch test)
  • the formulated test compound (0.002% active ingredient) was applied into a pouch which was previously equipped with a filter paper. After the application, wheat seeds (cv. Arina) were sown into the upper fault of the filter paper. The prepared pouches were then incubated at 23°C/18°C (day/night) and 80%r.h. One week after sowing, the wheat plants were inoculated by spraying a spore suspension (5xl0 5 conidia/ml) on the test plants. After an incubation period of lday at 23°C and 95%r.h. the plants were kept for 9days at 20°C/18°C (day/night) and 80%r.h. The disease incidence was assessed 8days after inoculation. The efficacy of each test compound is used as an indicator for systemic activity.
  • Example B-l 7 Action against Septoria tritici / wheat (Septoria leaf spot on wheat)
  • Compounds 14.202 or 14.210 each show good activity in this test ( ⁇ 20% disease incidence).

Abstract

The invention relates to a fungicidally active compound of formula (I): where Het is a 5- or 6-membered heterocyclic ring containing one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, provided that the ring is not 1,2,3-triazole, the ring being substituted by groups R8, R9 and R10; X is a single or double bond; Y is O, S, N(R11) or (CR12R13)(CR14R15)m(CR16R17)n; m is 0 or 1; n is 0 or 1; and R1 to R17 each, independently, have a range of values; to the preparation of these compounds, to novel intermediates used in the preparation of these compounds, to agrochemical compositions which comprise at least one of the novel compounds as active ingredient, to the preparation of the compositions mentioned and to the use of the active ingredients or compositions in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.

Description

HETEROCYCLOCARBOXAMIDE DERIVATIVES
The present invention relates to novel tricyclic amine derivatives which have microbiocidal activity, in particular fiingicidal activity. The invention also relates to the preparation of these compounds, to novel intermediates used in the preparation of these compounds, to agrochemical compositions which comprise at least one of the novel compounds as active ingredient, to the preparation of the compositions mentioned and to the use of the active ingredients or compositions in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.
The present invention provides a compound of formula (I):
Figure imgf000002_0001
where Het is a 5- or 6-membered heterocyclic ring containing one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, provided that the ring is not 1,2,3-triazole, the ring being substituted by groups R8, R9 and R10; X is a single or double bond; Y is O, S, N(Rπ) or (CR12R13)(CRI4R15)m(CR16R17)n; m is 0 or 1; n is 0 or 1; R1 is hydrogen, C alkyl, C haloalkyl, CM alkoxy, Cι-4haloalkoxy, CH2C≡CR18, CH2CRI9=CHR20, CH=C=CH2 or COR21; R2 and R3 are each, independently, hydrogen, halogen, C alkyl, Cι- alkoxy or CM haloalkoxy; R4, R5, R6 and R7 are each, independently, hydrogen, halogen, CM alkyl, CM haloalkyl, CM alkoxy, C haloalkoxy, CM -ϋkylthio, CM haloalkylthio, hydroxymethyl, CM alkoxymethyl, C(O)CH3 or C(O)OCH3; R8, R9 and R10 are each, independently, hydrogen, halogen, cyano, nitro, CM alkyl, CM haloalkyl, CM alkoxy( - )alkylene or C haloalkoxy(CM)alkylene, provided that at least one of R8, R9 and R10 is not hydrogen; R11 is hydrogen, CM alkyl, benzyl (in which the phenyl group is optionally substituted with up to three substituents, each independently selected from halogen, CM alkyl, C haloalkyl and C alkoxy), formyl, C(O)CM alkyl (optionally substituted by halogen or C alkoxy), C(=O)O-Cι-6 alkyl (optionally substituted by halogen, CM alkoxy or cyano) or CM alkoxy(Cι-4)alkylene; R12, R13, R14, R15, R16 and R17 are each, independently, hydrogen, halogen, hydroxy, Cι-6 alkyl, C2.6 alkenyl [both optionally substituted by halogen, hydroxy, CM alkoxy, =O, aryl or O-C(O)-CM alkyl or a 3-7 membered carboxylic ring (itself optionally substituted by up to three methyl groups)], a 3-7 membered saturated ring (optionally substituted by up to three methyl groups and optionally containing one heteroatom selected from nitrogen and oxygen) or CM alkoxy; or R12 and R13 together with the carbon atom to which they are attached form the group C=O or a 3-5 membered carbocyclic ring (optionally substituted by up to three methyl groups and optionally with up to 2 heteroatoms each independently selected from O and N); or R12 and R13 together form a Cι.6 alkylidene (optionally substituted by up to three methyl groups) or a C3.6 cycloalkylidene group (optionally substituted by up to three methyl groups); R18, R19 and R20 are each, independently, hydrogen, halogen, CM alkyl, CM haloalkyl or C alkoxy(Cι.4)alkylene; and R21 is hydrogen, -6 alkyl, Cj.6 haloalkyl, CM alkoxy(Cι-4 )alkylene, CM alkyl-S-(CM)alkylene, C alkoxy or aryl.
Halogen is fluoro, chloro, bromo or iodo; preferably fluoro, chloro or bromo. Each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, wo-propyl, sec-butyl, wo-butyl, tert-butyl, neø-pentyl, n-heptyl, 1,3-dimethylbutyl, 1,3-dimethylpentyl, l-methyl-3-ethyl-butyl or 1,3,3-trimethylbutyl. Likewise, each alkylene moiety is a straight or branched chain.
Haloalkyl moieties are alkyl moieties which are substituted by one or more of the same or different halogen atoms and are, for example, CF3, CF2C1, CHF2, CH2F, CC13, CF3CH2, CHF2CH2, CH2FCH2, CH3CHF or CH3CF2. Alkenyl and alkynyl moieties can be in the form of straight or branched chains.
Each alkenyl moiety, where appropriate, may be of either the (E)- or ©-configuration.
A 3-5 membered carbocyclic ring includes a spiro-three or five membered ring. Aryl includes phenyl, naphthyl, anthracyl, fluorenyl and indanyl but is preferably phenyl.
Alkylidene moieties may be in the form of straight or branched chains. Alkylidene includes methyϋdene [CH2=], ethylidene [CH3C(H)=], n-propylidene, -propylidene [(CH3)2C=], n-butylidene, -butylidene, 2-butylidene, n-pentylidene, j'-pentylidene, neø-pentylidene, 2-pentylidene, n-hexylidene, 2-hexylidene, 3-hexylidene, *-hexylidene and neo-hexylidene.
Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
Cycloalkenyl includes cyclobutenyl, cyclopentenyl, cyclohexenyl and cycloheptenyl. Cycloalkylidene includes cyclopropylidene [c(C3H4)=], cyclobutylidene, cyclopentylidene and cyclohexylidene.
In one aspect of the invention, R11 is hydrogen, CM alkyl, benzyl (in which the phenyl group is optionally substituted with up to three substituents, each independently selected from halogen, CM alkyl, CM haloalkyl and CM alkoxy), formyl, C(O)C alkyl or CM alkoxy(CM)alkylene.
In another aspect of the invention, R12, R13, R14, R15, R16 and R17 are each, independently, hydrogen, CM alkyl or CM alkoxy. Het is preferably pyrrolyl, pyrazolyl, thiazolyl, oxazolyl, pyridinyl, pyrimidyl, pyridazinyl, 2,3-dihydro-[l,4]oxathiine-6-yl, oxazinyl, thiazinyl or triazinyl.
Het is more preferably pyrrolyl, pyrazolyl, thiazolyl, oxazolyl, pyridinyl or 2,3-dibydro-[l,4]oxathiine-yl.
Het is even more preferably pyrrolyl, pyrazolyl, thiazolyl or pyridinyl. Het is most preferably pyrrolyl or pyrazolyl.
Preferably X is a single bond.
In one aspect, Y is O, S, N(Rn), CH2, CH2CH2, CH2CH2CH2, C(CH3)2, CH(CH3), CH(C2H5), C(CH3)(C2H5), CH(OCH3) or C(OCH3)2; more preferably N(R"), O, S, CH2, CH2CH2, CH2CH2CH2, C(CH3)2, CH(CH3) or CH(C2H5)^ even more preferably N(Rn), O, S, CH2 or CH2CH2; and still more preferably O, CH2 or N(Rn). Preferably Y is O, N(Rπ) or (CR12R13)(CR14R15)m(CRl6R17)π. More preferably Y is O or (CRl2R13)(CR14R,5)m(CRl6R17)n. Even more preferably Y is (CRl2R13)(CR14R15)ra(CR16R17)n. Still more preferably Y is (CR12R13). Preferably n is 0.
Preferably m is 0. Preferably R1 is hydrogen, CH2C≡CR18, CH=C=CH2 or COR21. More preferably R1 is hydrogen, CH2C≡CH, CH=C=CH2, C(O)H or C(O)CH3. Yet more preferably R1 is hydrogen, CH2C≡CH, CH=C=CH2 or C(O)CH3. Even more preferably R1 is hydrogen, CH2C≡CH or CH=C=CH2. Most preferably R1 is hydrogen. Preferably R2 is hydrogen, halogen or CM alkyl.
More preferably R2 is hydrogen or halogen. Most preferably R2 is hydrogen. Preferably R3 is hydrogen or methyl. More preferably R3 is hydrogen. Preferably R4 is hydrogen, CM alkyl, halogen, C haloalkyl, CM alkoxy, C(O)CH3 or C(O)OCH3.
More preferably R4 is hydrogen, Cι.2 alkyl, halogen, CF3, methoxy, C(O)CH3 or C(O)OCH3.
Even more preferably R4 is hydrogen, methyl, chlorine, CF3 or methoxy. Most preferably R4 is hydrogen or methyl.
Preferably R5 is hydrogen, CM alkyl, halogen, C haloalkyl, CM alkoxy, C(O)CH3 or C(O)OCH3.
More preferably R5 is hydrogen, C1-2 alkyl, chlorine, CF3, methoxy, C(O)CH3 or C(O)OCH3. Most preferably R5 is hydrogen or methyl.
Preferably R6 is hydrogen, CM alkyl, C alkoxy or C(O)CH3. More preferably R6 is hydrogen, methyl, methoxy or C(O)CH3. Most preferably R6 is hydrogen or methyl. Preferably R7 is hydrogen, CM alkyl, CM alkoxy or C(O)CH3. More preferably R7 is hydrogen, methyl, methoxy or C(O)CH3.
Most preferably R7 is hydrogen or methyl.
Preferably R8 is hydrogen, halogen, CM alkyl, CMhaloalkyl or methoxymethylene. More preferably R8 is hydrogen, chloro, fluoro, bromo, C1-2 alkyl, CF3, CF2C1, CHF2, CH2F or methoxymethylene. Even more preferably R8 is hydrogen, chloro, fluoro, Cι-2 alkyl, CF3, CF2C1, CHF2,
CH2F or methoxymethylene.
Most preferably R8 is hydrogen, chloro, fluoro, methyl, CF3, CHF2or CH2F. Preferably R9 is hydrogen, halogen, C alkyl or C haloalkyl or methoxymethylene.
More preferably R9 is hydrogen, chloro, fluoro, bromo, Cι-2 alkyl, CF3, CF2C1, CHF2, CH2F or methoxymethylene. Even more preferably R9 is hydrogen, chloro, fluoro, Cι-2 alkyl, CF3, CF2C1, CHF2,
CH2F or methoxymethylene.
Most preferably R9 is hydrogen, chloro, fluoro, methyl, CF3, CHF2 or CH2F. Preferably R10 is hydrogen, halogen, CM alkyl, CM aloalkyl or methoxymethylene. More preferably R10 is hydrogen, chloro, fluoro, bromo, Cj.2 alkyl, CF3, CF2C1, CHF2, CH2F or methoxymethylene.
Even more preferably R10 is hydrogen, chloro, fluoro, Cι.2 alkyl, CF3, CF2C1, CHF2, CH2F or methoxymethylene.
Most preferably R10 is hydrogen, chloro, fluoro, methyl, CF , CHF2 or CH2F. In one aspect of the invention R11 is hydrogen, CM alkyl, benzyl, formyl, C(O)CH3 or C(O)OC(CH3)3; more preferably hydrogen or Cι-2 alkyl.
Preferably R11 is C alkyl, formyl, C(O)CH3 or C(O)OCw alkyl (optionaUy substituted by halogen, CN or C alkoxy). More preferably R11 is C(O)OCι-4 alkyl.
In one aspect of the invention R12, R13, R14, R15, R16 and R17 are each, independently, hydrogen, d.2 alkyl or methoxy.
Preferably R12 and R13 are each, independently, hydrogen, halogen, .5 alkyl, -3 alkoxy, CH2OH, CH(O), -e cycloalkyl, CH2O-C(=O)CH3, CH2-C3.6 cycloalkyl or benzyl; or R12 and R13 together with the carbon atom to which they are attached form the group C=O or a 3-5 membered carbocyclic ring; or R12 and R13 together form C1-5 alkylidene or C3.6 cycloalkylidene.
More preferably R12 and R13 are, independently, H, CH3, C2H5, n-C3H7). /-C3H7, «-C H9, Λ,ec-C4H9, /-C4H9, CH(C2H5)2, CH2-cyclopropyl or cyclopentyl; or R12 and R13 together with the carbon atom to which they are attached form a 3-membered or 5-membered carbocyclic ring. Preferably R14 is H or CH3.
Preferably R15 is H or CH3. Preferably R16 is H or CH3. Preferably R17 is H or CH3.
Preferably R18 is hydrogen, chloro, bromo, methyl or methoxy.
More preferably R18 is hydrogen, chloro or methyl.
Most preferably R18 is hydrogen. Preferably R19 is hydrogen, chloro, bromo, methyl or methoxy.
More preferably R19 is hydrogen, chloro or methyl.
Most preferably R19 is hydrogen.
Preferably R20 is hydrogen, chloro, bromo, methyl or methoxy.
More preferably R20 is hydrogen, chloro or methyl. Most preferably R20 is hydrogen.
Preferably R21 is hydrogen, methyl, OC(CH3)3 or CH3OCH2.
Compounds of formula (C):
Figure imgf000007_0001
where Y, R4, R5, R6 and R7 are as defined above for a compound of formula (I) are useful as intermediates in the preparation of compounds of formula (I). Some Compounds of formula (C) are novel but some are already known.
Therefore, in another aspect, the present invention provides a compound of formula (C) where Y is O or S; and R4, R5, R6 and R7 are each C(O)OCH3; or Y is N(R' ') or (CR12R13)(CRl4R15)m(CRl0R,7)n; R4, R5, R6, R7, R14, R15, R16, R17, m and n are each as defined above for a compound of formula (I); R11 is benzyl (in which the phenyl group is optionally substituted with up to three substituents, each independently selected from halogen, CM alkyl, CM haloalkyl and CM alkoxy); and R12 and R13 together with the carbon atom to which they are attached form a 3-5 membered carbocyclic ring (optionally substituted by up to three methyl groups and containing 1 or 2 heteroatoms each independently selected from O and N). Compounds of formula (D):
Figure imgf000008_0001
where Y, R4, R5, R6 and R7 are as defined above for a compound of formula (I) are also useful as intermediates in the preparation of compounds of formula (I). Some Compounds of formula (D) are novel but some are already known. Therefore, in another aspect, the present invention provides a compound of formula (D) where Y is O or S; and R4, R5, R6 and R7 are each C(O)OCH3; or Y is N(R") or (CR12R13)(CR14R15)m(CR16R17)n; R4, R5, R6, R7, R14, R15, R16, R17, m and n are each as defined above for a compound of formula (I); Ru is benzyl (in which the phenyl group is optionally substituted with up to three substituents, each independently selected from halogen, C alkyl, CM haloalkyl and CM alkoxy) ; and R12 and R13 together with the carbon atom to which they are attached form a 3-5 membered carbocyclic ring (optionally substituted by up to three methyl groups and containing 1 or 2 heteroatoms each independently selected from O and N).
The compounds of formula (I), (C) and (D) may exist as different geometric or optical isomers or in different tautomeric forms. This invention covers, for each formula, all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.
The compounds in Tables 1 to 29 below illustrate compounds of the invention. Table 1 provides 94 compounds of formula (C) wherein Y, R4, R5, R6 and R7 are as defined in Table 1.
Table 1
Figure imgf000008_0002
Figure imgf000009_0001
Figure imgf000010_0001
Table 2 provides 111 compounds of formula (D) wherein Y, R4, R5, R6 and R7 are defined in Table 2.
Table 2
Figure imgf000010_0002
Figure imgf000011_0001
Figure imgf000012_0001
Table Z represents Table 3 [when Z is 3], Table 4 [when Z is 4], Table 5 [when Z is 5], Table 6 [when Z is 6] , Table 7 [when Z is 7], Table 8 [when Z is 8], Table 9 [when Z is 9], Table 10 [when Z is 10], Table 11 [when Z is 11], Table 12 [when Z is 12] , Table 13 [when Z is 13], Table 14 [when Z is 14], Table 15 [when Z is 15], Table 16 [when Z is 16], Table 17 [when Z is 17], Table 18 [when Z is 18], Table 19 [when Z is 19], Table 20 [when Z is 20], Table 21 [when Z is 21], Table 22 [when Z is 22], Table 23 [when Z is 23], Table 24 [when Z is 24], Table 25 [when Z is 25], Table 26 [when Z is 26], Table 27 [when Z is 27], Table 28 [when Z is 28] and represents Table 29 [when Z s 29]. X is either a single bond (-) or a double bond (=).
Table Z
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0003
Table 3 provides 235 compounds of formula (I) where Het is
Figure imgf000017_0001
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 3. Table 4 provides 235 compounds of formula (I) where Het is
Figure imgf000017_0002
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 4. Table 5 provides 235 compounds of formula (I) where Het is
Figure imgf000018_0001
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 5. Table 6 provides 235 compounds of formula (I) where Het is
Figure imgf000018_0002
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 6. Table 7 provides 235 compounds of formula (I) where Het is
Figure imgf000018_0003
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 7. Table 8 provides 235 compounds of formula (I) where Het is
Figure imgf000018_0004
H3
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 8. Table 9 provides 235 compounds of formula (I) where Het is
H3C
tf N
I
CH, R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 9. Table 10 provides 235 compounds of formula (I) where Het is
Figure imgf000018_0005
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 10. Table 11 provides 235 compounds of formula (I) where Het is
Figure imgf000019_0001
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 11. Table 12 provides 235 compounds of formula (I) where Het is
Figure imgf000019_0002
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 12. Table 13 provides 235 compounds of formula (I) where Het is
Figure imgf000019_0003
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 13. Table 14 provides 235 compounds of formula (I) where Het is
CF,
to N '
I
CH,
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 14. Table 15 provides 235 compounds of formula (I) where Het is
Figure imgf000019_0004
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 15. Table 16 provides 235 compounds of formula (I) where Het is
CFH,
to*
N
I
CH,
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 16. Table 17 provides 235 compounds of formula (I) where Het is
Figure imgf000020_0001
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 17. Table 18 provides 235 compounds of formula (I) where Het is
Figure imgf000020_0002
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 18. Table 19 provides 235 compounds of formula (I) where Het is
Figure imgf000020_0003
H3
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 19. Table 20 provides 235 compounds of formula (I) where Het is
Figure imgf000020_0004
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 20. Table 21 provides 235 compounds of formula (I) where Het is
Figure imgf000020_0005
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 21. Table 22 provides 235 compounds of formula (I) where Het is
Figure imgf000021_0001
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 22. Table 23 provides 235 compounds of formula (I) where Het is
H-C
CH3
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 23. Table 24 provides 235 compounds of formula (I) where Het is
Figure imgf000021_0002
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 24. Table 25 provides 235 compounds of formula (I) where Het is
Figure imgf000021_0003
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 25. Table 26 provides 235 compounds of formula (I) where Het is
Figure imgf000021_0004
R2 and R3 are both hydrogen; and X, Y, Rl, R4, R5, R6 and R7 are as defined in Table 26. Table 27 provides 235 compounds of formula (I) where Het is
Figure imgf000021_0005
R2 and R , 33 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 27. Table 28 provides 235 compounds of formula (I) where Het is
Figure imgf000022_0001
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 28. Table 29 provides 235 compounds of formula (I) where Het is
Figure imgf000022_0002
R2 and R3 are both hydrogen; and X, Y, R1, R4, R5, R6 and R7 are as defined in Table 29.
Throughout this description, temperatures are given in degrees Celsius; "NMR" means nuclear magnetic resonance spectrum; MS stands for mass spectrum; and "%" is percent by weight, unless corresponding concentrations are indicated in other units; "syn" refers to a syn configuration of the relevant substituent with respect to the armellated benzene ring; and "anti" refers to an anti configuration of the relevant substituent with respect to the armellated benzene ring.
The following abbreviations are used throughout this description: m.p. = melting point b.p.= boiling point. s = singlet br = broad d = doublet dd = doublet of doublets t = triplet q = quartet m = multiplet ppm = parts per million
Table 30 shows selected melting point and selected NMR data, all with CDC13 as the solvent (unless otherwise stated; if a mixture of solvents is present, this is indicated as, for example, [CDC13 / d6-DMSO]), (no attempt is made to list all characterising data in all cases) for compounds of Tables 1 to 29.
Table 30
Figure imgf000022_0003
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0002
The compounds according to formula (I) may be prepared according to the following reaction schemes. Preparation of a compound of formula (I)
Figure imgf000034_0001
A compound of formula (I) [where R1 is hydrogen; and Het, R2, R3, R4, R5, R6, R7, X and Y are as defined above for a compound of formula (I)] may be synthesized by reacting a compound of (II) [where Het is as defined above for a compound of formula (I) and R' is C,.5 alkyl] with an aniline of formula (III) [where R2, R3, R4, R5, R6, R7, X and Y are as defined above for a compound of formula (I)] in the presence of NaN(TMS)2 at -10°C to ambient temperature, preferably in dry THF, as described by J. Wang et al. Synlett, 2001, 1485. Scheme 2
Figure imgf000035_0001
Alternatively, a compound of formula (I) [where R1 is hydrogen; and Het, R2, R3, R4, R5, R6, R7, X and Y are as defined above for a compound of formula (I)] may be prepared by reacting a compound of formula (II') [where Het is as defined above for a compound of formula (I)] with an aniline of formula (III) [where R2, R3, R4, R5, R6, R7, X and Y are as defined above for a compound of formula (I)] in the presence of an activating agent [such as BOP-C1] and two equivalents of a base [such as triethylamine] or by reacting a compound of formula (II") [where Het is as defined above for a compound of formula (I); and Q is Cl, F or Br] which is obtained from a compound of formula (IF) by treatment with a halogenating agent such as thionyl chloride, oxalyl chloride, phosgene, SF4, DAST, Deoxofluor or thionlylbromide, with an aniline of formula (III) [where R2, R3, R4, R5, R6, R7, X and Y are as defined above for a compound of formula (I)] in the presence of one equivalent of base [such as NEt3, NaHCO3, KHCO3, Na2CO3 or K2CO3] in a solvent [such as dichloromethane, ethyl acetate or DMF] preferably at -10 to 30°C.
Figure imgf000035_0002
Furthermore a compound of formula (I) [where Rl is hydrogen; and Het, R2 to R7, X and Y are as defined for a compound of formula (I)] is reacted with a species Z-R1 [where R1 is as defined for formula (I), except that it is not hydrogen; and Z is preferably Cl, Br or I; or Z is such that Z-R1 is an anhydride, that is, when R1 is COR*, Z is
OCOR*] in the presence of a base [for example NaH, NEt3, NaHCO3 or K2CO3] in an appropriate solvent [such as ethyl acetate] or in a biphasic mixture [such as dichloromethane /water mixture], at -10 to 30°C. Starting Materials Heterocyclic acids and esters [that is, compounds of formula (II') or (II)] are generally known from the literature or may be synthesized according to known methods. Ortbo-substituted aminobenzonorbonenes (including homologues) of formula (C) or (D) (scheme 4) may be accomplished through Diels-Alder addition of an in situ generated benzyne [for example starting from a 6-nitroanthranilic acid of formula (A), as described by L.Paquette et al, J. Amer. Chem. Soc. 99, 3734 (1977) or from other suitable precursers (see H. Pellissier et al. Tetrahedron, 59, 701 (2003)] to a 5-7 membered cyclic 1 ,4-diene to give a nitro-benzonorbornadiene of formula (B) according to or by analogy to L.Paquette et al, J. Amer. Chem. Soc. 99, 3734 (1977), D. Gravel et al. Can. J. Chem. 69, 1193 (1991), J.R. Malpass et al. Tetrahedron , 48, 861 (1992), D.E. Lewis et al. Synthetic Communications, 23, 993 (1993), R.N. Warrener et al. Molecules, 6, 353
(2001), R.N. Warrener et al. Molecules, 6, 194 (2001) or I. Fleming et al. J. Chem. Soc, Perkin Trans.1, 2645 (1998). Suitable aprotic solvents for this step include ethyl acetate, dichloromethane, acetone, THF and dimethoxyethane. Reaction temperatures range from room temperature to 100°C, preferably 40-80°C. Subsequent selective reduction of the nitro-group in a compound of formula (B) to give an amino-benzonorbornadiene of formula (C) requires mild conditions [for example, either metallic zinc in the presence of ammonium chloride, or aluminium amalgam]. Both methods work in protic solvents such as ethanol, water or mixtures thereof. Alternatively a compound of formula (C) may also be obtained from a compound of formula (B) by catalytic hydrogen reduction with a modified 5% Pt/C catalyst at elevated pressure (~10bar) and elevated temperature (~100°C) in toluene- water. Catalytic reduction under standard conditions (for example 5% Pd C or 5% Ra Ni or 5% Rh/C) in a solvent [such as methanol, ethanol, THF or ethyl acetate] reduces both the nitro-group and the double bond to furnish a benzonorbornene of formula (D). Preferred reaction conditions are ambient temperature and normal pressure.
Scheme 4
Figure imgf000037_0001
Some of the compounds of formulae (B), (C) and (D) are described in the literature
[see, for example, L. A Paquette et al., J. Amer. Chem Soc. 99, 3134 (1977); D. Gravel et al., Canad. J. Chem. 69, 1193 (1991); T. Nishiyama et al., Rikagaku-hen, 28, 37 (2000); H. Plieninger et al., Chem. Ber. 109, 2121 (1976); and A. J. Kirby et al, J. Chem. Soc, Perkin Trans. 2, 1997, 1081]. Novel starting materials of formulae (C) or (D) may be synthesized by analogy to scheme 4 or according to the literature cited above.
Surprisingly, it has now been found that the novel compounds of formula (I) have, for practical purposes, a very advantageous spectrum of activities for protecting plants against diseases that are caused by fungi as well as by bacteria and viruses. The compounds of formula (I) can be used in the agricultural sector and related fields of use as active ingredients for controlling plant pests. 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 are 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.
It is also possible to use compounds of formula (I) as dressing agents for the treatment of plant propagation material, in particular of seeds (fruit, tubers, grains) and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
Furthermore the compounds according to present invention may 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, etc.
The compounds of formula (I) are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Hekninthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e.g. Nenturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes classes (e.g. Phytophthora, Pythium, Plasmopara). Outstanding activity has been observed against powdery mildew (Erysiphe spp.). Furthermore, the novel compounds of formula I are effective against phytopathogenic bacteria and viruses (e.g. against Xanthomonas spp, Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus).
Within the scope of present invention, target crops to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamomum, camphor) or plants such as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals. The compounds of formula (I) are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they are conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects. Suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO97/33890. The compounds of formula (I) are normally used in the form of 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 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) can be mixed with other fungicides, resulting in some cases in unexpected synergistic activities. Mixing components which are particularly preferred are azoles, such as azaconazole, BAY 14120, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibencon- azole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole; pyrimidinyl carbinole, such as ancymidol, fenarimol, nuarimol; 2-amino-pyrimidines, such as bupirimate, dimethirimol, ethirimol; morpholines, such as dodemorph, fenpropidine, fenpropimorph, spiroxamine, tridemorph; anilinopyrimidines, such as cyprodinil, mepanipyrim, pyrimethanil; pyrroles, such as fenpiclonil, fludioxonil; phenylamides, such as benalaxyl, fiiralaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl; benzimidazoles, such as benomyl, carbendazim, debacarb, fuberidazole, thiabendazole; dicarboximides, such as chlozolinate, dichlozoline, iprodione, myclozoline, procymidone, vinclozoline; carboxamides, such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, thifluzamide; guanidines, such as guazatine, dodine, iminoctadine; strobilurines, such as azoxystrobin, kresoxim-methyl, metomi- nostrobin, SSF-129, trifloxystrobin, picoxystrobin, BAS 500F (proposed name pyraclostrobin), BAS 520; dithiocarbamates, such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram; N-halomethylthiotetrahydrophthalimides, such as captafol, captan, dichlofluanid, fluoromides, folpet, tolyfluanid; Cu-compounds, such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper, oxine-copper; nitrophenol-derivatives, such as dinocap, nitrothal-isopropyl; organo-p-derivatives, such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos, tolclofos-methyl; various others, such as acibenzolar-S-methyl, anilazine, benthiavalicarb, blasticidin-S, chinomethionate, chloroneb, chlorothalonil, cyflufenamid, cymoxanil, dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, SYP-LI90 (proposed name: flumorph), dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, fentin, ferimzone, fluazinam, flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, iprovalicarb, IKF-916 (cyazofamid), kasugamycin, methasulfocarb, metrafenone, nicobifen, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole, triforine, validamycin, zoxamide (RH7281).
A preferred method of applying 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. However, the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, for example 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 [that is, a composition containing the compound of formula (I)] and, if desired, a solid or liquid adjuvant, is 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).
The agrochemical formulations will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the compound of formula I, 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant.
Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from lOg to 1kg a.i./ha, most preferably from 20g to 600g a.i./ha. When used as seed drenching agent, convenient dosages are from lOmg to lg of active substance per kg of seeds. Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.
The following non-limiting Examples illustrate the above-described invention in more detail.
EXAMPLE 1 This Example illustrates the preparation of Compound No. 2.01.
A solution of l,4-dimethyl-5-nitro-l,4-dihydro-l,4-epoxynaphthalene (5.49g; 25.27mmol) (see T. Nishiyama et al., Rikagaku-hen, 28, 37-43 (2000)) in THF (55ml) was hydrogenated in the presence of RaNi (l.lg) at ambient temparature. Hydrogen uptake was 2.231itres (97%) after lδhours. After filtering off the catalyst the filtrate was evaporated and taken up into ether, washed with an aqueous NaHCO3-solution and dried (NaSO ) to give 4.60g of crude product as an oil. Trituration with hexane and a trace of ether furnished a total of 4.51g (94%) of reddish crystalline product.
EXAMPLE 2 This Example illustrates the preparation of Compound No. 1.01. To l,4-dimethyl-5-nitro-l,4-dihydro-l,4-epoxynaphthalene (4.22g; 19.43mmol)
(see Example 1) in ethanol (60ml) was added a solution of ammoniumchloride (2.08g) in water (5.2ml) at 47°C. Under vigorous stirring, zinc powder (9.10g; 0.14mol) was added in portions over a period of 5minutes. The suspension was heated to reflux for 5'/2hours followed by filtration through Hyflo™ to give a clear yellow filtrate. After evaporation the crude product amounted 4.57g of a viscous oil. Column chro matography on silica gel in ethyl acetate-hexane (1:4) gave 1.24g (34%) of the desired product as brownish crystals.
EXAMPLE 3 This Example illustrates the preparation of Compound No. 2.16. A solution of 5-nitrobenzonorbornadiene (L.A. Paquette et al., J. Amer. Chem. Soc. 99, 3734 (1977)) (2.52g; 13.46mmol) in methanol (100ml) was hydrogenated in the presence of 5% Pd/C (0.5g) at ambient temperature. H2-uptake was 1.141itres (95%) after 11 minutes. The solution was filtered from the catalyst and evaporated to give pure product (1.86g; 87% ) as a yellow oil, which solidified on standing at room temperature (m.p. 63-64°C).
EXAMPLE 4 This Example illustrates the preparation of Compound No. 3.023.
A solution of l-methyl-4-trifluoromethyl-lH-pyrrole-3-carboxylic acid (1.02g; 5.3 mmol) and a catalytic amount of DMF (3drops) in dichloromethane (20ml) was reacted under initial ice cooling with oxalyl chloride (0.805g; 1.2eq.) for 2hours. Within 15minutes, the reaction mixture was then added dropwise to a solution of 1,8-dimethyl- 1 l-oxa-tricyclo[6.2.1.0*2,7*]undeca-2,4,6-trien-3-ylamine (Compound No. 2.01 ; see preparation above) (l.Og; 5.284mmol) and triethylamine (1.07g; 10.57mmol) in 20ml dichloromethane under cooling (3-7°C) with subsequent stirring at ambient temperature for 3' hours. The reaction mixture was then poured on to ice water and extracted with dichloromethane to give 2.26g of crude product. Purification on silica gel in ethyl acetate-hexane (1: 1) followed by trituration with ether-hexane furnished a solid ( 1.14g; 59%) as a mixture of isomers.
EXAMPLE 5
This Example illustrates the preparation of Compound No.3.024. A suspension of NaH (0.107g; 60% oil dispersion, ~2.7mmol) in DMF (5ml) was reacted with a solution of 1 -methyl-4-trifluoromethyl- 1 H-pyrrole-3-carboxylic acid( 1 ,8- dimethyl-1 l-oxa-tricyclo[6.2.1.0*2,7*]undeca-2,4,6-trien-3-yl)-amide (Compound No. 3.023; see preparation above) (0.65g; 1.784mmol) in 5ml DMF at 10-15°C for 30minutes. 3-Bromo-l-propyne (0.276g; 2.32mmol) was added and the mixture was further reacted overnight at ambient temperature. After aqueous work up with ice water and ethyl acetate and purification on silica gel 0.36g (50%) of the desired product as a mixture of isomers were obtained.
FORMULATION EXAMPLES FOR COMPOUNDS OF FORMULA (I) Working procedures for preparing formulations of the compounds of formula I such as Emulsifiable Concentrates, Solutions, Granules, Dusts and Wettable Powders are described in WO97/33890. BIOLOGICAL EXAMPLES: FUNGICIDAL ACTIONS
Example B-l: Action against Puccinia recondita / wheat (Brownrust on wheat)
1 week old wheat plants cv. Arina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the wheat plants are inoculated by spraying a spore suspension (lxl05uredospores/ml) on the test plants. After an incubation period of 2 days at 20°C and 95%r.h. the plants are kept in a greenhouse for 8days at 20°C and 60%r.h. The disease incidence is assessed 10 days after inoculation.
Infestation is prevented virtually completely (0-5% infestation) with each of Compounds 3.048, 14.048, 29.048, 15.048, 20.048, 3.028, 22.048, 21.048, 15.023, 15.027, 15.028, 3.035, 14.035, 15.035, 15.052, 14.210, 15.210, 14.202 and 15.202. Example B-2: Action against Podosphaera leucotricha / apple (Powdery mildew on apple)
5 week old apple seedlings cv. Mclntosh are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after, the application apple plants are inoculated by shaking plants infected with apple powdery mildew above the test plants. After an incubation period of 12 days at 22°C and 60%r.h. under a light regime of 14/10hours (light/dark) the disease incidence is assessed.
Compounds 3.048, 14,048, 15.048, 22.048, 14.210, 15.210, 14.202, 15.202 and 15.023 each exhibit strong efficacy (<20% infestation). Example B-3: Action against Nenturia inaequalis / apple ("Scab on apple)
4 week old apple seedlings cv. Mclntosh are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the apple plants are inoculated by spraying a spore suspension (4xl05conidia/ml) on the test plants. After an incubation period of 4 days at 21°C and 95%r.h. the plants are placed for 4 days at 21°C and 60%r.h. in a greenhouse. After another 4 day incubation period at 21°C and 95%r.h. the disease incidence is assessed. Compounds 3.048, 14.048, 14.210, 15.210, 14.202, 15.202 and 15.048 each exhibit strong efficacy (<20% infestation). Example B-4: Action against Erysiphe graminis / barley (Powdery mildew on barley)
1 week old barley plants cv. Regina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the barley plants are inoculated by shaking powdery mildew infected plants above the test plants. After an incubation period of 6 days at 20°C / 18°C (day/night) and 60%r.h. in a greenhouse the disease incidence is assessed.
Compounds 3.023, 14.023, 3.048, 14.048, 15.048, 3.027, 3.028, 15.023, 14.210, 15.210, 14.202, 15.202 and 15.027 each exhibit strong efficacy (<20% infestation). Example B-5: Action against Botrytis cinerea / grape (Botrytis on grapes)
5 week old grape seedlings cv. Gutedel are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the grape plants are inoculated by spraying a spore suspension (lxl06conidia/ml) on the test plants. After an incubation period of 4 days at 21°C and 95%r.h. in a greenhouse the disease incidence is assessed.
Compounds 14.048, 15.048, 3.028, 14.210, 15.210, 14.202, 15.202 and 15.027 each show good activity in this test (<50% disease incidence). Example B-6: Action against Botrytis cinerea / tomato (Botrytis on tomatoes)
4 week old tomato plants cv. Roter Gnom are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the tomato plants are inoculated by spraying a spore suspension (lxl05conidia/ml) on the test plants. After an incubation period of 4 days at 20°C and 95%r.h. in a growth chamber the disease incidence is assessed.
Compounds 3.048, 3.052, 14.052, 15.048, 14.210, 15.210, 14.202, 15.202 and 15.023 each exhibit good efficacy (<50% disease incidence).
Example B-7: Action against Septoria nodorum / wheat (Septoria leaf spot on wheat . 1 week old wheat plants cv. Arina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the wheat plants are inoculated by spraying a spore suspension (5xl05conidia/ml) on the test plants. After an incubation period of 1 day at 20°C and 95%r.h. the plants are kept for 10 days at 20°C and 60%r.h. in a greenhouse. The disease incidence is assessed 11 days after inoculation. Compounds 3.002, 3.048, 14.048, 14.210, 15.210, 14.202, 15.202 and 15.048 each show good activity in this test (<50% disease incidence). Example B-8: Action against Helminthosporium teres / barley (Net blotch on barley)
1 week old barley plants cv. Regina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the barley plants are inoculated by spraying a spore suspension (3xl04conidia/ ml) on the test plants. After an incubation period of 4 days at 20°C and 95%r.h. in a greenhouse the disease incidence is assessed.
Compounds 3.023, 14.023, 3.048, 14.048, 15.048, 3.027, 15.023, 15.027, 14.210, 15.210, 14.202, 15.202 and 15.028 each show good activity in this test (<20% disease incidence). Example B-9: Action against Alternaria solani / tomato (Early blight on tomatoes)
4 week old tomato plants cv. Roter Gnom are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the tomato plants are inoculated by spraying a spore suspension (2xl05conidia/ml) on the test plants. After an incubation period of 3days at 20°C and 95%r.h. in a growth chamber the disease incidence is assessed.
Compounds 3.023, 14.023, 3.048, 14.048, 14.210, 15.210, 14.202, 15.202 and 15.048 each show good activity in this test (<20% disease incidence). Example B-10: Action against Uncinula necator / grape (Powdery mildew on grapes) 5week old grape seedlings cv. Gutedel are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the grape plants are inoculated by shaking plants infected with grape powdery mildew above the test plants. After an incubation period of 7days at 26°C and 60%r.h. under a light regime of 14/10hours (light/dark) the disease incidence is assessed.
Compounds 14.048, 15.048, 14.028 and 15.023 each show good activity in this test (<20% disease incidence). Example B-l 1: Systemic Action against Erysiphe graminis / barley (Powdery mildew on barley) (Pouch test)
The formulated test compound (0.002% active ingredient) is applied into a pouch which was previously equipped with a filter paper. After the application barley seeds (cv.Express) are sown into the upper fault of the filter paper. The prepared pouches are then incubated at 23°C/18°C (day/night) and 80%r.h. One week after sowing barley plants were inoculated by shaking powdery mildew infected plants above the test plants.
After an incubation period of 6days the disease incidence was assessed. The efficacy of each test compound is used as an indicator for systemic activity. Compounds 14.024, 3.002, 3.048, 29.048, 3.027, 22.048, 21.048, 15.023, 15.027,
15.028 and 15.035 each show good activity in this test (<50% disease incidence).
Example B-l 2: Action against Fusarium culmorum / wheat (Fusarium head blight on wheat) (Pouch test)
A conidia suspension of F. culmorum (7xl05conidia/ml) is mixed with the formulated test compound (0.002% active ingredient). The mixture is applied into a pouch which was previously equipped with a filter paper. After the application wheat seeds (cv.Orestis) are sown into the upper fault of the filter paper. The prepared pouches are then incubated for 1 ldays at ca.10-18° C and 100%r.h. with a daily light period of
14hours. The evaluation is made by assessing the degree of disease occurrence in the form of brown lesions on the roots.
Compounds 14.024, 15.048, 20.048, 14.027, 24.048 and 3.035 each show good activity in this test (<50% disease incidence).
Example B-13: Action Gaeumannomyces graminis / wheat (Take- all on wheat) (pouch test) A defined amount of mycelium of G. graminis is mixed with water. The formulated test compound (0.002% active ingredient) is added to the mycelium suspension. The mixture is applied into a pouch which was previously equipped with a filter paper. After the application wheat seeds (cv.Orestis) are sown into the upper fault of the filter paper.
The prepared pouches are then incubated for 14days at 18°C/16°C (day/night) and 80%r.h. with a daily light period of 14hours. The evaluation is made by assessing the degree of root browning. Compounds 15.048, 20.048, 21.048, 15.028 and 15.052 each show good activity in this test (<50% disease incidence).
Example B-14: Action against Puccinia recondita / wheat (Brownrust on wheat) (Pouch test) Formulated test compound (0.002% active ingredient) is applied into a pouch which was previously equipped with a filter paper. After the application wheat seeds (cv.Arina) are sown into the upper fault of the filter paper. The prepared pouches are then incubated at 23°C/18°C (day/night) and 80%r.h. One week after sowing, the wheat plants were inoculated by spraying a spore suspension (lxl05uredospores/ml) on the test plants. After an incubation period of lday at 23°C and 95%r.h. the plants were kept for 9days at 20°C/18°C (day/night) and 80%r.h . The disease incidence was assessed lOdays after inoculation. The efficacy of each test compound is used as an indicator for systemic activity.
Compounds 14.024, 3.002, 14.002, 15.048, 20.048, 3.027, 22.048, 15.023, 15.027, 15.028, 3.035, 14.035 and 15.035 each show good activity in this test (<50% disease incidence).
Example B-15: Action against Rhizoctonia solani / rice (Sheath blight on rice) (Pouch test)
A defined amount of mycelium of R. solani is mixed with water. The formulated test compound (0.002% active ingredient) is added to the mycelium suspension. The mixture is applied into a pouch which was previously equipped with a filter paper. After the application rice seeds (cv.Koshihikari) are sown into the upper fault of the filter paper. The prepared pouches are then incubated for lOdays at 23°C/21°C (day/night) and 100%r.h. with a daily light period of 14hours. The evaluation is made by assessing the degree of disease occurrence in the form of brown lesions on the roots.
Compounds 3.048, 14.048, 29.048, 3.052, 29.052, 14.052, 15.048, 20.048, 3.027, 14.028, 22.048, 21.048, 4.048, 15.023, 3.035, 14.035 and 15.035 each show good activity in this test (<50% disease incidence). Example B-16: Action against Septoria nodorum / wheat (Septoria leaf spot on wheat) .Pouch test)
The formulated test compound (0.002% active ingredient) was applied into a pouch which was previously equipped with a filter paper. After the application, wheat seeds (cv. Arina) were sown into the upper fault of the filter paper. The prepared pouches were then incubated at 23°C/18°C (day/night) and 80%r.h. One week after sowing, the wheat plants were inoculated by spraying a spore suspension (5xl05conidia/ml) on the test plants. After an incubation period of lday at 23°C and 95%r.h. the plants were kept for 9days at 20°C/18°C (day/night) and 80%r.h. The disease incidence was assessed 8days after inoculation. The efficacy of each test compound is used as an indicator for systemic activity.
Compounds 3.048, 29.048, 15.048, 14.027, 15.023 and 15.027 each show good activity in this test (<50% disease incidence). Example B-l 7: Action against Septoria tritici / wheat (Septoria leaf spot on wheat)
2 week old wheat plants cv. Riband are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, wheat plants are inoculated by spraying a spore suspension (10xl05conidia/ml) on the test plants. After an incubation period of 1 day at 23°C and 95% r.h., the plants are kept for 16 days at 23°C and 60% r.h. in a greenhouse. The disease incidence is assessed 18 days after inoculation.
Compounds 14.202 or 14.210 each show good activity in this test (<20% disease incidence).

Claims

A compound of formula (I):
Figure imgf000049_0001
where Het is a 5- or 6-membered heterocyclic ring containing one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, provided that the ring is not 1,2,3-triazole, the ring being substituted by groups R8, R9 and R10; X is a single or double bond; Y is O, S, N(Rn) or (CR12R,3)(CR14R15)m(CR16R17)n; m is 0 or 1; n is 0 or 1; R1 is hydrogen, 01-43 !, Cι-4 haloalkyl, C alkoxy, CM haloalkoxy, CH2C≡CR18, CH2CRI9=CHR20, CH=C=CH2 or COR21; R2 and R3 are each, independently, hydrogen, halogen, C1-4 alkyl, C alkoxy or d -4 haloalkoxy; R4, R5, R6 and R7 are each, independently, hydrogen, halogen, CM alkyl, CMhaloalkyl, C alkoxy, CM haloalkoxy, CMalkylthio, C haloalkylthio, hydroxymethyl, C,-4 alkoxymethyl, C(O)CH3 or C(O)OCH3; R8, R9 and R10 are each, independently, hydrogen, halogen, cyano, nitro, CM alkyl, C haloalkyl, Cι- alkoxy(Cι-4)alkylene or CM haloalkoxy(CM)alkylene, provided that at least one of R8, R9 and R10 is not hydrogen; R11 is hydrogen, CM alkyl, benzyl (in which the phenyl group is optionally substituted with up to three substituents, each independently selected from halogen, CM alkyl, CMhaloalkyl and C alkoxy), formyl, C(0)CM alkyl (optionally substituted by halogen or C alkoxy), C(=O)O-Cι-6 alkyl (optionally substituted by halogen, C alkoxy or cyano) or C alkoxy(C )alkylene; R12, R13, R14, R15, R16 and R17 are each, independently, hydrogen, halogen, hydroxy, C].6 alkyl, C2.6 alkenyl [both optionally substituted by halogen, hydroxy, C alkoxy, =O, aryl or O-C(O-CM alkyl or a 3-7 membered carboxylic ring (itself optionally substituted by up to three methyl groups)], a 3-7 membered saturated ring (optionally substituted by up to three methyl groups and optionally containing one heteroatom selected from nitrogen and oxygen) or d-4 alkoxy; or R12 and R13 together with the carbon atom to which they are attached form the group C=O or a 3-5 membered carbocyclic ring (optionally substituted by up to three methyl groups and optionally with up to 2 heteroatoms each independently selected from
O and N); or R12 and R13 together form a Cι.6 alkylidene (optionally substituted by up to three methyl groups) or a C3.6 cycloalkylidene group (optionally substituted by up to three methyl groups); R18, R19 and R20 are each, independently, hydrogen, halogen, CM alkyl, CM haloalkyl or CM alkoxy(C )alkylene; and R21 is hydrogen, Cι-6 alkyl, Cι_s haloalkyl,
CM alkoxy(Cι-4 )alkylene, CM alkyl-S-(CM. alky_εne, CM alkoxy or aryl.
2. A compound of formula (I) as claimed in claim 1 where Het is pyrrolyl, pyrazolyl, thiazolyl, oxazolyl, pyridinyl, pyrimidyl, pyridazinyl, 2,3-dihydro-[l,4]oxathϋne-6-yl, oxazinyl, thiazinyl or triazinyl.
3. A compound of formula (I) as claimed in claim 1 or 2 where Y is O, N(R' ') or (CRl2R,3)(CR14R15)m(CRl0R,7)„.
4. A compound of formula (I) as claimed in claim 1, 2 or 3 where R1 is hydrogen, CH2C≡CR18, CH=C=CH2 or COR21.
A compound of formula (I) as claimed in claim 1, 2, 3 or 4 where R2 is hydrogen, halogen or CM alkyl.
A compound of formula (I) as claimed in claim 1, 2, 3, 4 or 5 where R3 is hydrogen or methyl.
7. A compound of formula (C):
Figure imgf000051_0001
where Y is O or S; and R4, R5, R6 and R7 are each C(O)OCH3; or Y isN(R") or (CR12R13)(CR14R15)m(CR16Rl7)n; R4, R5, R6, R7, R14, R15, R16, R17, m and n are each as defined in claim 1 ; R1 ' is benzyl (in which the phenyl group is optionally substituted with up to three substituents, each independently selected from halogen, CM alkyl, C haloalkyl and CM alkoxy); and R12 and R13 together with the carbon atom to which they are attached form a 3-5 membered carbocyclic ring (optionally substituted by up to three methyl groups and containing 1 or 2 heteroatoms each independently selected from O and N).
8. A compound of formula (D):
Figure imgf000051_0002
where Y is O or S; and R4, R5, R6 and R7 are each C(O)OCH3; or Y isN(Rπ) or (CRI2Rl3)(CR14R15)m(CRI6R17)n; R4, R5, R6, R7, R14, R15, R16, R17, m and n are each as defined in claim 1 ; Rn is benzyl (in which the phenyl group is optionally substituted with up to three substituents, each independently selected from halogen, CM alkyl, CM haloalkyl and CM alkoxy); and R12 and R13 together with the carbon atom to which they are attached form a 3-5 membered carbocyclic ring (optionally substituted by up to three methyl groups and containing 1 or 2 heteroatoms each independently selected from O and N).
9. A composition for controlling microorganisms and preventing attack and infestation of plants therewith, wherein the active ingredient is a compound of formula (I) as claimed in claim 1 together with a suitable carrier.
10. A method of controlling or preventing infestation of cultivated plants by phytopathogenic microorganisms by application of a compound of formula (I) as claimed in claim 1 to plants, to parts thereof or the locus thereof.
PCT/EP2003/011388 2002-10-18 2003-10-14 Heterocyclocarboxamide derivatives WO2004035589A1 (en)

Priority Applications (26)

Application Number Priority Date Filing Date Title
JP2004544232A JP4607591B2 (en) 2002-10-18 2003-10-14 Heterocyclocarboxamide derivatives
MEP-2008-316A ME00223B (en) 2002-10-18 2003-10-14 Heterocyclocarboxamide derivatives
AT03772217T ATE460418T1 (en) 2002-10-18 2003-10-14 HETEROCYCLOCARBOXAMIDE DERIVATIVES
EP03772217A EP1556385B1 (en) 2002-10-18 2003-10-14 Heterocyclocarboxamide derivatives
YU20050297A RS51937B (en) 2002-10-18 2003-10-14 Heterocyclocarboxamide derivatives
EA200500574A EA010264B1 (en) 2002-10-18 2003-10-14 Heterocyclocarboxamide derivatives
SI200331806T SI1556385T1 (en) 2002-10-18 2003-10-14 Heterocyclocarboxamide derivatives
NZ539376A NZ539376A (en) 2002-10-18 2003-10-14 Heterocyclocarboxamide derivatives
AU2003280376A AU2003280376B2 (en) 2002-10-18 2003-10-14 Heterocyclocarboxamide derivatives
US10/530,737 US7598395B2 (en) 2002-10-18 2003-10-14 Heterocyclocarboxamide derivatives
MEP-316/08A MEP31608A (en) 2002-10-18 2003-10-14 Heterocyclocarboxamide derivatives
UAA200504639A UA81784C2 (en) 2002-10-18 2003-10-14 Derivatives of heterocycliccarboxylamides, composition for control of microorganisms and methods for control of phytopathogenic microorganisms
DE60331670T DE60331670D1 (en) 2002-10-18 2003-10-14 Heterocyclocarboxamidderivate
MXPA05003899A MXPA05003899A (en) 2002-10-18 2003-10-14 Heterocyclocarboxamide derivatives.
CA2498851A CA2498851C (en) 2002-10-18 2003-10-14 Heterocyclocarboxamide derivatives
BRPI0314875-0A BR0314875B1 (en) 2002-10-18 2003-10-14 HETEROCYCLOCARBOXAMIDE DERIVATIVES, AND COMPOSITION AND METHOD TO CONTROL OR AVOID PLANT INFESTATION BY PHYTOPATHOGENIC MICROORGANISMS
DK03772217.0T DK1556385T3 (en) 2002-10-18 2003-10-14 Heterocyclocarboxamid derivatives
IL167290A IL167290A (en) 2002-10-18 2005-03-07 Heterocyclocarboxamide derivatives
EGNA2005000128 EG24050A (en) 2002-10-18 2005-04-12 Heterocylocarboxamide derivatives
TNP2005000112A TNSN05112A1 (en) 2002-10-18 2005-04-18 HETEROCYCLOCARBOXAMIDE DERIVATIVES
NO20052201A NO331404B1 (en) 2002-10-18 2005-05-04 Heterocycle carboxamide derivatives, composition with such derivatives, intermediates and methods for controlling plant attacks
HRP20050441AA HRP20050441B1 (en) 2002-10-18 2005-05-17 Heterocyclocarboxamide derivatives
HK06104366.2A HK1082254A1 (en) 2002-10-18 2006-04-11 Heterocyclocarboxamide derivatives
IL190341A IL190341A (en) 2002-10-18 2008-03-20 Heterocyclocarboxamide derivatives, compositions comprising them and a method of controlling or preventing infestation of cultivated plants by the application thereof
US12/549,478 US7994093B2 (en) 2002-10-18 2009-08-28 Heterocyclocarboxamide derivatives
FR18C1024C FR18C1024I2 (en) 2002-10-18 2018-06-05 HETEROCYCLOCARBOXAMIDE DERIVATIVES

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0224316.0 2002-10-18
GBGB0224316.0A GB0224316D0 (en) 2002-10-18 2002-10-18 Chemical compounds

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US10/530,737 A-371-Of-International US7598395B2 (en) 2002-10-18 2003-10-14 Heterocyclocarboxamide derivatives
US12/549,478 Continuation US7994093B2 (en) 2002-10-18 2009-08-28 Heterocyclocarboxamide derivatives

Publications (1)

Publication Number Publication Date
WO2004035589A1 true WO2004035589A1 (en) 2004-04-29

Family

ID=9946176

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/011388 WO2004035589A1 (en) 2002-10-18 2003-10-14 Heterocyclocarboxamide derivatives

Country Status (39)

Country Link
US (2) US7598395B2 (en)
EP (1) EP1556385B1 (en)
JP (1) JP4607591B2 (en)
KR (2) KR100858013B1 (en)
CN (1) CN100448876C (en)
AR (1) AR041649A1 (en)
AT (1) ATE460418T1 (en)
AU (1) AU2003280376B2 (en)
BE (1) BE2013C039I2 (en)
BR (1) BR0314875B1 (en)
CA (1) CA2498851C (en)
CR (1) CR7727A (en)
CY (1) CY1110077T1 (en)
DE (1) DE60331670D1 (en)
DK (1) DK1556385T3 (en)
EA (2) EA015708B1 (en)
EC (1) ECSP055675A (en)
EG (1) EG24050A (en)
ES (1) ES2342714T3 (en)
FR (1) FR18C1024I2 (en)
GB (1) GB0224316D0 (en)
GE (2) GEP20115347B (en)
HK (1) HK1082254A1 (en)
HR (1) HRP20050441B1 (en)
IL (2) IL167290A (en)
MA (1) MA27405A1 (en)
ME (2) ME00223B (en)
MX (1) MXPA05003899A (en)
NO (1) NO331404B1 (en)
NZ (1) NZ539376A (en)
PL (1) PL221973B1 (en)
PT (1) PT1556385E (en)
RS (1) RS51937B (en)
SI (1) SI1556385T1 (en)
TN (1) TNSN05112A1 (en)
TW (1) TWI319704B (en)
UA (1) UA81784C2 (en)
WO (1) WO2004035589A1 (en)
ZA (1) ZA200501870B (en)

Cited By (99)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004091482A3 (en) * 2003-04-07 2004-12-23 Glaxo Group Ltd M3 muscarinic acetylcholine receptor antagonists
WO2006037632A1 (en) * 2004-10-08 2006-04-13 Syngenta Participations Ag Synergistic fungicidal compositions
WO2007009717A1 (en) * 2005-07-18 2007-01-25 Syngenta Participations Ag Pyrazole-4- carboxamide derivatives as microbiocides
WO2007031323A1 (en) 2005-09-16 2007-03-22 Syngenta Participations Ag. Process for the production of amides
WO2007048556A1 (en) * 2005-10-25 2007-05-03 Syngenta Participations Ag Heterocyclic amide derivatives useful as microbiocides
WO2007068417A2 (en) * 2005-12-12 2007-06-21 Syngenta Participations Ag Process for the preparation of amines
WO2007115765A1 (en) * 2006-04-06 2007-10-18 Syngenta Participations Ag Fungicidal compositions
WO2007124907A2 (en) * 2006-04-27 2007-11-08 Syngenta Participations Ag Heterocyclyl-carboxylic acid (benzonorbornene-5-yl)amide derivatives as fungicides for agrochemical use
WO2008009405A2 (en) 2006-07-17 2008-01-24 Syngenta Participations Ag Novel pyridazine derivatives
WO2008017443A1 (en) * 2006-08-08 2008-02-14 Syngenta Participations Ag Process for the production of aromatic amines in the presence of a palladium complex comprising a ferrocenyl biphosphine ligand
WO2008049584A1 (en) 2006-10-25 2008-05-02 Syngenta Participations Ag Novel pyridazine derivatives
JP2008524163A (en) * 2004-12-15 2008-07-10 ギリンデュス アクチェンゲゼルシャフト Synthesis of phosphitylated compounds using quaternary heterocyclic activators
WO2008098928A2 (en) * 2007-02-14 2008-08-21 Basf Se Method of inducing virus tolerance of plants
WO2008113447A2 (en) 2007-03-16 2008-09-25 Syngenta Limited Novel solid forms of a microbiocide
WO2007118069A3 (en) * 2006-04-07 2008-11-06 Syngenta Participations Ag Method of controlling phytopathogenic diseases on turfgrass
WO2008131901A1 (en) 2007-04-25 2008-11-06 Syngenta Participations Ag Fungicidal compositions
WO2009010260A2 (en) 2007-07-16 2009-01-22 Syngenta Participations Ag Condensed anthranilamide insecticides
WO2009024341A2 (en) 2007-08-22 2009-02-26 Syngenta Participations Ag, Condensed anthran i lami de derivatives as insectisides
EP2053045A1 (en) 2007-10-26 2009-04-29 Syngenta Participations AG Novel imidazole derivatives
EP2053046A1 (en) 2007-10-26 2009-04-29 Syngeta Participations AG Novel imidazole derivatives
EP2053044A1 (en) 2007-10-26 2009-04-29 Syngenta Participations AG Novel imidazole derivatives
US7531559B2 (en) 2002-08-22 2009-05-12 Syngenta Crop Protection, Inc. Fungicidal 1,2,3 triazole derivatives
WO2009090039A1 (en) 2008-01-16 2009-07-23 Syngenta Participations Ag Pyridazine fungicides
US20090221588A1 (en) * 2006-04-06 2009-09-03 Syngenta Crop Protection, Inc. Fungicidal compositions
US7723371B2 (en) 2005-11-15 2010-05-25 Syngenta Crop Protection, Inc. Microbiocides
WO2010072632A1 (en) 2008-12-24 2010-07-01 Syngenta Limited Methods for the preparation of aryl amides
EP2213167A1 (en) 2006-01-16 2010-08-04 Syngenta Participations AG Anthranilamide derivatives and their use for the control of insects and acari
WO2010086103A2 (en) 2009-01-30 2010-08-05 Bayer Cropscience Aktiengesellschaft Use of succinate dehydrogenase inhibitors for controlling powdery mildew primary infections
WO2010091803A2 (en) 2009-02-13 2010-08-19 Bayer Cropscience Ag Use of succinate dehydrogenase inhibitors for extending shelf life of fruits and vegetables
WO2010100008A2 (en) 2009-03-06 2010-09-10 Syngenta Participations Ag Fungicidal compositions
WO2010102866A1 (en) 2009-03-12 2010-09-16 Syngenta Participations Ag Imidazole derivatives
WO2010130532A1 (en) 2009-05-15 2010-11-18 Syngenta Limited Process for purification of 1-methylpyrazole-4-carboxylic acid esters
EP2255626A1 (en) 2009-05-27 2010-12-01 Bayer CropScience AG Use of succinate dehydrogenase inhibitors to increase resistance of plants or parts of plants to abiotic stress
WO2011006603A2 (en) 2009-07-16 2011-01-20 Bayer Cropscience Ag Synergistic active substance combinations containing phenyl triazoles
WO2011012620A2 (en) 2009-07-31 2011-02-03 Syngenta Participations Ag Processes for the alkylation of pyrazoles
WO2011012618A2 (en) 2009-07-28 2011-02-03 Syngenta Participations Ag Processes relating to the alkylation of pyrazoles
WO2011015416A1 (en) * 2009-08-06 2011-02-10 Syngenta Participations Ag Process for the preparation of pyrazole carboxylic acid amides
WO2011032657A2 (en) 2009-09-16 2011-03-24 Bayer Cropscience Ag Use of succinate dehydrogenase inhibitors for increasing the content of desired ingredients in crops
EP2319319A1 (en) 2007-09-20 2011-05-11 Basf Se Combinations comprising a fungicidal strain and at least one additional fungicide
WO2011069893A1 (en) 2009-12-08 2011-06-16 Basf Se Pesticidal mixtures
WO2011069890A2 (en) 2009-12-08 2011-06-16 Basf Se Pesticidal mixtures
WO2011076501A1 (en) 2009-12-22 2011-06-30 Syngenta Participations Ag Novel 5-(pyridin-3-yl)-pyridanize derivatives and their use as microbicides
WO2011082913A1 (en) 2010-01-08 2011-07-14 Syngenta Participations Ag Fungicidal compositions containing isopyrazam, azoxystrobin and cyproconazole
US20110178310A1 (en) * 2008-05-14 2011-07-21 Syngenta Crop Protection, Inc. Process for the preparation of amides
EP2353387A1 (en) 2010-02-05 2011-08-10 Bayer CropScience AG Use of succinate dehydrogenase (SDH) inhibitors in the treatment of plant types in the sweet grass family
WO2011095461A1 (en) 2010-02-04 2011-08-11 Syngenta Participations Ag Pyridazine derivatives, processes for their preparation and their use as fungicides
WO2011095459A1 (en) 2010-02-04 2011-08-11 Syngenta Participations Ag Pyridazine derivatives, process for their preparation and their use as fungicides
WO2011104183A1 (en) 2010-02-24 2011-09-01 Syngenta Participations Ag Novel microbicides
WO2011113788A1 (en) 2010-03-15 2011-09-22 Syngenta Participations Ag Process for purifying 3-difluoromethyl-1-methyl-1h-pyrazole-4-carboxylic acid
WO2011113789A1 (en) 2010-03-15 2011-09-22 Syngenta Participations Ag Process for preparing alkyl 2-alkoxymethylene-4,4-difluoro-3-oxobutyrates
EP2377397A1 (en) 2010-04-14 2011-10-19 Bayer CropScience AG Use of fungicidal agents for controlling mycoses in palm trees
WO2011147953A1 (en) 2010-05-28 2011-12-01 Basf Se Pesticidal mixtures
WO2012001040A1 (en) 2010-07-02 2012-01-05 Syngenta Participations Ag Novel microbiocidal dioxime ether derivatives
WO2012013590A2 (en) 2010-07-26 2012-02-02 Bayer Cropscience Ag Use of succinate dehydrogenase inhibitors and/or respiratory chain complex iii inhibitors for improving the ratio of harmful to beneficial microorganisms
WO2012013754A1 (en) 2010-07-29 2012-02-02 Syngenta Participations Ag Novel microbiocidal dioxime ether derivatives
WO2012020776A1 (en) 2010-08-10 2012-02-16 住友化学株式会社 Plant disease control composition and application for same
WO2012019950A1 (en) 2010-08-10 2012-02-16 Syngenta Participations Ag Process for the preparation of 3-haloalkylpyrazoles
WO2012041874A1 (en) 2010-10-01 2012-04-05 Syngenta Participations Ag Fungicidal compositions
WO2012052544A1 (en) 2010-10-21 2012-04-26 Syngenta Limited Agrochemical concentrates containing isopyrazam
WO2012055864A1 (en) 2010-10-27 2012-05-03 Solvay Sa Process for the preparation of pyrazole-4-carboxamides
WO2012065932A1 (en) 2010-11-15 2012-05-24 Bayer Cropscience Ag Decahydro-1,4-methanonaphthalen carboxamides
WO2012066122A1 (en) 2010-11-18 2012-05-24 Syngenta Participations Ag 2 - (pyridin- 2 -yl) -quinazoline derivatives and their use as microbicides
WO2012065947A1 (en) 2010-11-15 2012-05-24 Bayer Cropscience Ag 5-halogenopyrazolecarboxamides
WO2012065945A1 (en) 2010-11-15 2012-05-24 Bayer Cropscience Ag 5-halogenopyrazole(thio)carboxamides
WO2012069652A2 (en) 2010-11-26 2012-05-31 Syngenta Participations Ag Fungicide mixtures
WO2012110464A1 (en) 2011-02-17 2012-08-23 Bayer Cropscience Ag Use of sdhi fungicides on conventionally bred asr-tolerant, stem canker resistant and/or frog-eye leaf spot resistant soybean varieties
US20120302559A1 (en) * 2010-02-05 2012-11-29 Rotam Agrochem International Co., Ltd. Method for treating fungal infections, fungicidal compositions and their use
WO2012175511A1 (en) 2011-06-21 2012-12-27 Bayer Intellectual Property Gmbh Method for producing pyrazolylcarboxanilides
WO2013011010A1 (en) 2011-07-19 2013-01-24 Syngenta Participations Ag Fungizide mixtures
WO2013026866A2 (en) 2011-08-23 2013-02-28 Syngenta Participations Ag Novel microbiocides
AU2013201962B2 (en) * 2007-04-25 2013-08-01 Syngenta Participations Ag Fungicidal compositions
EP2662364A1 (en) * 2012-05-09 2013-11-13 Bayer CropScience AG Pyrazole tetrahydronaphthyl carboxamides
WO2013167548A1 (en) * 2012-05-09 2013-11-14 Bayer Cropscience Ag Pyrazole tetrahydronaphthyl carboxamides
WO2014060177A1 (en) 2012-10-16 2014-04-24 Syngenta Participations Ag Fungicidal compositions
WO2014078849A1 (en) 2012-11-19 2014-05-22 Lonza, Inc. Succinate dehydrogenase inhibitor containing compositions
WO2014083088A2 (en) 2012-11-30 2014-06-05 Bayer Cropscience Ag Binary fungicidal mixtures
WO2014095677A1 (en) * 2012-12-19 2014-06-26 Bayer Cropscience Ag Difluoromethyl-nicotinic- tetrahydronaphtyl carboxamides
WO2014095826A1 (en) 2012-12-18 2014-06-26 Bayer Cropscience Ag Binary fungicidal and bactericidal combinations
WO2014095678A1 (en) * 2012-12-19 2014-06-26 Bayer Cropscience Ag Tetrahydronaphthyl(thio) carboxamides
US8859558B2 (en) 2010-06-07 2014-10-14 Dow Agrosciences, Llc. Pyrazinyl carboxamides as fungicides
US8871679B2 (en) 2008-07-04 2014-10-28 Basf Se Fungicidal mixtures comprising substituted 1-methylpyrazol-4-ylcarboxanilides
US9012360B2 (en) 2009-03-25 2015-04-21 Bayer Intellectual Property Gmbh Synergistic combinations of active ingredients
US20160000067A1 (en) * 2010-07-27 2016-01-07 Syngenta Limited Formulations
US9232794B2 (en) 2009-06-02 2016-01-12 Bayer Intellectual Property Gmbh Use of succinate dehydrogenase inhibitors for controlling Sclerotinia ssp
EP2980078A1 (en) 2014-07-29 2016-02-03 Solvay SA Process for the preparation of pyrazole-4-carboxamides
EP3150069A1 (en) 2009-12-22 2017-04-05 Mitsui Chemicals Agro, Inc. Plant disease control composition and method for controlling plant disease by applying the same
WO2017129759A1 (en) 2016-01-28 2017-08-03 Solvay Sa Halogen substituted diketones, pyrazole compounds and processes for the manufacture of pyrazole compounds
WO2017194517A1 (en) 2016-05-10 2017-11-16 Solvay Sa Composition comprising 3-(haloalkyl or formyl)-1h-pyrazole-4-carboxylic acids or esters, its manufacture and its use for the preparation of carboxamides
WO2018024644A1 (en) 2016-08-02 2018-02-08 Solvay Sa Manufacture of hydrazinyl compounds useful in the manufacture of pyrazole carboxylic acid and derivatives, hydrazinyl compounds and their use
WO2018083281A1 (en) 2016-11-07 2018-05-11 Solvay Sa Process for the manufacture of carboxylic acids or carboxylic acid derivatives
WO2018202677A1 (en) 2017-05-02 2018-11-08 Solvay Sa Process for the manufacture of carboxylic acids or carboxylic acid derivatives
EP3495351A1 (en) 2017-12-08 2019-06-12 Solvay Sa Oxidation of a pyrazolyl ketone compound to the corresponding carboxylic acid
WO2019122164A1 (en) 2017-12-22 2019-06-27 Solvay Sa Process for the manufacture of pyrazole carboxylic derivatives and precursors thereof
WO2019122194A1 (en) 2017-12-22 2019-06-27 Solvay Sa Process for the manufacture of iminium compounds and their application in the manufacture of pyrazole derivatives
WO2019122204A1 (en) 2017-12-22 2019-06-27 Solvay Sa Process for the manufacture of pyrazole compounds
EP3586631A2 (en) 2008-02-05 2020-01-01 Basf Se Plant health composition
WO2021138315A1 (en) * 2020-01-03 2021-07-08 Blue Oak Pharmaceuticals, Inc. Compounds and compositions for treating cns disorders
US11491133B2 (en) 2017-08-02 2022-11-08 Sunovion Pharmaceuticals Inc. Heteroaryl-isochroman compounds and uses thereof
US11560384B2 (en) 2017-05-04 2023-01-24 University Of Utah Research Foundation Benzonorbornadiene derivatives and reactions thereof

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101415327B (en) * 2006-04-07 2012-10-10 先正达参股股份有限公司 Method of controlling phytopathogenic diseases on turfgrass
DK2081884T3 (en) * 2006-09-28 2013-08-05 Syngenta Participations Ag Process for the preparation of amines
JP5860471B2 (en) * 2010-11-15 2016-02-16 バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングBayer Intellectual Property GmbH N-arylpyrazole (thio) carboxamides
EP2662370A1 (en) * 2012-05-09 2013-11-13 Bayer CropScience AG 5-Halogenopyrazole benzofuranyl carboxamides
JP6020905B2 (en) * 2012-11-01 2016-11-02 国立大学法人横浜国立大学 Novel compounds and plant resistance inducers
CN103891724B (en) * 2012-12-31 2015-09-30 江苏丰登作物保护股份有限公司 A kind of composite synergistic bactericidal composition and application thereof containing isopyrazam and oxime bacterium ester
CN103891725B (en) * 2012-12-31 2016-04-06 江苏丰登作物保护股份有限公司 A kind of bactericidal composition and application thereof containing isopyrazam and kresoxim-methyl
CN103210930B (en) * 2013-05-23 2014-10-29 陕西上格之路生物科学有限公司 Isopyrazam-containing sterilizing composition
EP3016949B1 (en) 2013-07-02 2020-05-13 Syngenta Participations AG Pesticidally active bi- or tricyclic heterocycles with sulfur containing substituents
EP2873668A1 (en) 2013-11-13 2015-05-20 Syngenta Participations AG. Pesticidally active bicyclic heterocycles with sulphur containing substituents
CN104649973B (en) 2013-11-25 2017-02-15 沈阳中化农药化工研发有限公司 Pyrazole amide compound and application thereof
EP3083643B1 (en) 2013-12-20 2019-02-27 Syngenta Participations AG Pesticidally active substituted 5,5-bicyclic heterocycles with sulphur containing substituents
CN106508945B (en) * 2016-11-11 2019-02-19 山东农业大学 A kind of bactericidal composition and its preparation and application containing isopyrazam and iprodione
CN109380236A (en) * 2017-08-07 2019-02-26 江苏龙灯化学有限公司 A kind of bactericidal composition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000009482A1 (en) * 1998-08-12 2000-02-24 Syngenta Participations Ag Trifluoro methylpyrrol carboxamides
WO2001049664A1 (en) * 1999-12-29 2001-07-12 Syngenta Participations Ag Trifluoromethylpyrrole carboxamides and trifluoromethylpyrrolethioamides as fungicides
WO2001053259A1 (en) * 2000-01-21 2001-07-26 Syngenta Participations Ag Pyrrolecarboxamides and pyrrolethioamides as fungicides
WO2002066470A1 (en) * 2001-01-12 2002-08-29 Amgen Inc. Substituted alkylamine derivatives and methods of use

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2950308A (en) * 1959-10-28 1960-08-23 Dow Chemical Co Adducts of benzoquinonedimines
US3268581A (en) * 1964-05-08 1966-08-23 Dow Chemical Co Anthraquinone dialkanesulfonimide
EP0199822B1 (en) * 1984-10-29 1990-01-10 Sumitomo Chemical Company, Limited Pyrazolecarboxamide derivatives, process for their preparation, and bactericides containing them as effective ingredients
JPS62249966A (en) 1986-04-22 1987-10-30 Sumitomo Chem Co Ltd N-indanylamide derivative and fungicide containing same as active ingredient
ES2011602T3 (en) 1986-08-12 1994-07-16 Mitsubishi Chem Ind DERIVATIVES OF PIRIDINE CARBOXAMIDE AND ITS USE AS FUNGICIDES.
US4837242A (en) 1987-01-20 1989-06-06 Sumitomo Chemical Company, Limited Thiazoles and pyrazoles as fungicides
US4914097A (en) 1987-02-25 1990-04-03 Mitsubishi Kasei Corporation N-indanyl carboxamide derivative and agricultural/horticultural fungicide containing the derivative as active ingredient
JPH01117864A (en) 1987-07-02 1989-05-10 Sumitomo Chem Co Ltd Substituted nicotinic acid derivative, its production and agricultural and horticultural fungicide containing said derivative as active component
JPH01230569A (en) * 1987-11-06 1989-09-14 Sumitomo Chem Co Ltd Substituted carboxylic acid derivative, its production and agricultural and horticulatural fungicide containing said derivative as active component
JP2638966B2 (en) * 1987-11-06 1997-08-06 住友化学工業株式会社 Substituted thiazolecarboxylic acid derivatives and agricultural and horticultural fungicides containing the same as active ingredients
JPS6470479A (en) 1987-09-10 1989-03-15 Sumitomo Chemical Co Heterocylic carboxylic acid derivative, production thereof and agricultural and horticultural germicide containing said derivative as active ingredient
US4877441A (en) 1987-11-06 1989-10-31 Sumitomo Chemical Company Ltd. Fungicidal substituted carboxylic acid derivatives
JP2625871B2 (en) 1988-04-27 1997-07-02 住友化学工業株式会社 Substituted dihydropyrancarboxylic acid derivatives and agricultural and horticultural fungicides containing the same as active ingredients
JP2582863B2 (en) 1988-06-13 1997-02-19 三菱化学株式会社 Gray mold control agent containing N-indanylcarboxylic acid amide derivative as active ingredient
JPH0240374A (en) 1988-07-28 1990-02-09 Sumitomo Chem Co Ltd Substituted heterocyclic carboxylic acid derivative, production thereof and agricultural and horticultural fungicide comprising the same derivative as active ingredient
JPH0240384A (en) 1988-07-28 1990-02-09 Sumitomo Chem Co Ltd Substituted heterocyclic carboxylic acid derivative, production thereof and agricultural and horticultural fungicide comprising the same derivative as active ingredient
US5049575A (en) 1988-11-10 1991-09-17 Sumitomo Chemical Company Substituted carboxylic acid, fungicidal compositions and use
JP2639025B2 (en) * 1988-12-02 1997-08-06 住友化学工業株式会社 Substituted pyrazole carboxylic acid derivatives and agricultural and horticultural fungicides containing the same as active ingredients
JPH02157366A (en) 1988-12-12 1990-06-18 Hideo Saito Circulating sky parking equipment
JPH0454173A (en) 1990-06-20 1992-02-21 Mitsubishi Kasei Corp Optically active n-indanyl thiazolecarboxylic acid amide derivative and agricultural/horticultural bactericide with the same as active ingredient
US5093347A (en) * 1991-01-28 1992-03-03 Monsanto Company 3-difluoromethylpyrazolecarboxamide fungicides, compositions and use
EP0654464A1 (en) 1993-10-22 1995-05-24 Shell Internationale Researchmaatschappij B.V. Processes for the preparation of pesticides and intermediates
DE19544800A1 (en) * 1995-12-01 1997-06-05 Bayer Ag Process for the preparation of 1,3-dimethyl-5-fluoro-pyrazole-4-carboxanilides
DE19629828A1 (en) * 1996-07-24 1998-01-29 Bayer Ag Carbanilides
JP3645661B2 (en) 1996-07-25 2005-05-11 日本電気エンジニアリング株式会社 Mark reader
JPH1140384A (en) 1997-07-15 1999-02-12 Matsushita Electric Works Ltd Discharge lamp lighting device
JP4054173B2 (en) 2000-12-04 2008-02-27 富士フイルム株式会社 camera
GB0101996D0 (en) 2001-01-25 2001-03-14 Syngenta Participations Ag Organtic compounds

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000009482A1 (en) * 1998-08-12 2000-02-24 Syngenta Participations Ag Trifluoro methylpyrrol carboxamides
WO2001049664A1 (en) * 1999-12-29 2001-07-12 Syngenta Participations Ag Trifluoromethylpyrrole carboxamides and trifluoromethylpyrrolethioamides as fungicides
WO2001053259A1 (en) * 2000-01-21 2001-07-26 Syngenta Participations Ag Pyrrolecarboxamides and pyrrolethioamides as fungicides
WO2002066470A1 (en) * 2001-01-12 2002-08-29 Amgen Inc. Substituted alkylamine derivatives and methods of use

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
A.J.KIRBY ET AL., CHEMICAL SOCIETY, PERKIN TRANSACTIONS, no. 2, - 1997, pages 1081 - 1093, XP009026772 *
DATABASE CROSSFIRE BEILSTEIN [online] Beilstein Institut zur Förderung der Chemischen Wissenschaften, Frankfurt am Main, DE; XP002271778, Database accession no. 7269102 (BRN) *
DATABASE CROSSFIRE BEILSTEIN [online] Beilstein Institut zur Förderung der Chemischen Wissenschaften, Frankfurt am Main, DE; XP002271779, Database accession no. 4803445 (BRN) *
GRAVEL, D. ET AL., CANADIAN JOURNAL OF CHEMISTRY, vol. 69, no. 8, - 1991, pages 1193 - 1200 *
H.PLIENINGER ET AL: "Synthese von benz[c,d]indol-derivaten", CHEMISCHE BERICHTE, vol. 109, - 1976, pages 2121 - 2125, XP009026773 *
ODA, MASATSUGU ET.AL.: "structure activity relationships of 2-Chloropyridine-3-carboxamide fungicides", JOURNAL OF PESTICIDE SCIENCE (INT.ED.), no. 18, - 1993, pages 49 - 57, XP009026800 *
PLIENINGER, H. ET AL., CHEMISCHE BERICHTE, no. 109, - 1976, pages 2126 - 2139 *
ROBERT A. SNOW ET AL: "Analysis of bridging regioselectivity operative in photorearrangement of ortho-substituted benzonorbornadienes", JOURNAL OF THE AMERICAN CHEM. SOCIETY, vol. 99, no. 11, - 1977, pages 3734 - 3744, XP002271785 *

Cited By (232)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7531559B2 (en) 2002-08-22 2009-05-12 Syngenta Crop Protection, Inc. Fungicidal 1,2,3 triazole derivatives
US7956194B2 (en) 2002-08-22 2011-06-07 Syngenta Crop Protection, Inc. Microbiocidal (E.G. fungicidal) 1,2,3-triazole derivatives
EP2258690A1 (en) * 2002-08-22 2010-12-08 Syngenta Participations AG Tricyclic amines as intermediates in the synthesis of fungicidal carboxamide derivatives
US7232841B2 (en) 2003-04-07 2007-06-19 Glaxo Group Limited M3 muscarinic acetylcholine receptor antagonists
JP2006522161A (en) * 2003-04-07 2006-09-28 グラクソ グループ リミテッド M3 muscarinic acetylcholine receptor antagonist
WO2004091482A3 (en) * 2003-04-07 2004-12-23 Glaxo Group Ltd M3 muscarinic acetylcholine receptor antagonists
JP2008515834A (en) * 2004-10-08 2008-05-15 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト Synergistic bactericidal composition
CN101611715B (en) * 2004-10-08 2013-03-13 辛根塔参与股份公司 Synergistic fungicidal compositions
US8124566B2 (en) 2004-10-08 2012-02-28 Syngenta Crop Protection, Inc. Synergistic fungicidal compositions
US8124567B2 (en) 2004-10-08 2012-02-28 Syngenta Crop Protection, Inc. Fungicidal compositions
AU2005291423B2 (en) * 2004-10-08 2011-04-21 Syngenta Participations Ag Synergistic fungicidal compositions
EA013074B1 (en) * 2004-10-08 2010-02-26 Зингента Партисипейшнс Аг Synergistic fungicidal compositions
CN101622994B (en) * 2004-10-08 2013-01-09 辛根塔参与股份公司 Synergistic fungicidal compositions
NO338388B1 (en) * 2004-10-08 2016-08-15 Syngenta Participations Ag Fungicidal preparations and the use of these to protect beneficial plants
EP2347655A1 (en) 2004-10-08 2011-07-27 Syngenta Participations AG. Synergistic fungicidal compositions
TWI407909B (en) * 2004-10-08 2013-09-11 Syngenta Participations Ag Fungicidal compositions
KR101276549B1 (en) * 2004-10-08 2013-06-25 신젠타 파티서페이션즈 아게 Synergistic fungicidal compositions
CN101622993B (en) * 2004-10-08 2013-01-09 辛根塔参与股份公司 Synergistic fungicidal compositions
WO2006037632A1 (en) * 2004-10-08 2006-04-13 Syngenta Participations Ag Synergistic fungicidal compositions
JP2008524163A (en) * 2004-12-15 2008-07-10 ギリンデュス アクチェンゲゼルシャフト Synthesis of phosphitylated compounds using quaternary heterocyclic activators
WO2007009717A1 (en) * 2005-07-18 2007-01-25 Syngenta Participations Ag Pyrazole-4- carboxamide derivatives as microbiocides
JP2009501742A (en) * 2005-07-18 2009-01-22 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト Pyrazole-4-carboxamide derivatives as microbicides
US8003626B2 (en) 2005-07-18 2011-08-23 Syngenta Crop Protection, Inc. Pyrazole-4-carboxamide derivatives as microbiocides
CN101962364B (en) * 2005-09-16 2013-01-09 先正达参股股份有限公司 Process for the production of amides
EA013638B1 (en) * 2005-09-16 2010-06-30 Синджента Партисипейшнс Аг. Process for the production of amides
CN101277938B (en) * 2005-09-16 2012-01-11 先正达参股股份有限公司 Process for the production of amides
WO2007031323A1 (en) 2005-09-16 2007-03-22 Syngenta Participations Ag. Process for the production of amides
US7994341B2 (en) 2005-09-16 2011-08-09 Syngenta Limited Process for the production of amides
JP2009509935A (en) * 2005-09-16 2009-03-12 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト Method for producing amide
EP2253622A1 (en) 2005-09-16 2010-11-24 Syngenta Participations AG. Process for the production of amides
AU2006291419B2 (en) * 2005-09-16 2012-06-14 Syngenta Limited. Process for the production of amides
US8680337B2 (en) 2005-09-16 2014-03-25 Sungenta Limited Process for the production of amides
EP2253623A1 (en) 2005-09-16 2010-11-24 Syngenta Participations AG. New crystal form of a pyrazole fungicide
US8207207B2 (en) 2005-10-25 2012-06-26 Syngenta Crop Protection Llc Heterocyclic a amide derivatives useful as microbiocides
US8183416B2 (en) 2005-10-25 2012-05-22 Syngenta Crop Protection, Inc. Heterocyclic amide derivatives useful as microbiocides
EA014297B1 (en) * 2005-10-25 2010-10-29 Зингента Партисипейшнс Аг Heterocyclic amide derivatives useful as microbiocides
NO340774B1 (en) * 2005-10-25 2017-06-19 Syngenta Participations Ag Heterocyclic amide derivatives for use as microbiocides
CN102153478B (en) * 2005-10-25 2012-07-11 先正达参股股份有限公司 Heterocyclic amide derivatives useful as microbiocides
WO2007048556A1 (en) * 2005-10-25 2007-05-03 Syngenta Participations Ag Heterocyclic amide derivatives useful as microbiocides
JP2009516646A (en) * 2005-10-25 2009-04-23 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト Heterocyclic amide derivatives useful as microbicides
KR101343303B1 (en) * 2005-10-25 2013-12-23 신젠타 파티서페이션즈 아게 Heterocyclic amide derivatives useful as microbiocides
US7732469B2 (en) 2005-10-25 2010-06-08 Syngenta Crop Protection, Inc. Heterocyclic amide derivatives useful as microbiocides
US7723371B2 (en) 2005-11-15 2010-05-25 Syngenta Crop Protection, Inc. Microbiocides
EP2316813A1 (en) 2005-12-12 2011-05-04 Syngenta Participations AG Process for the preparation of amines
WO2007068417A3 (en) * 2005-12-12 2007-10-04 Syngenta Participations Ag Process for the preparation of amines
WO2007068417A2 (en) * 2005-12-12 2007-06-21 Syngenta Participations Ag Process for the preparation of amines
EP2316814A1 (en) 2005-12-12 2011-05-04 Syngenta Participations AG Process for preparation of halogen substituted benzonorbornenes derivatives
EP2316815A1 (en) 2005-12-12 2011-05-04 Syngenta Participations AG Process for preparation of halogen substituted arynes
KR101364220B1 (en) 2005-12-12 2014-02-21 신젠타 파티서페이션즈 아게 Process for the preparation of amines
EA014275B1 (en) * 2005-12-12 2010-10-29 Синджента Партисипейшнс Аг Process for the production of 5-aminobenzonorbornen derivatives
JP2009518346A (en) * 2005-12-12 2009-05-07 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト Method for preparing amines
US7781615B2 (en) 2005-12-12 2010-08-24 Syngenta Crop Protection, Inc. Process for the preparation of amines
EP2316809A1 (en) 2005-12-12 2011-05-04 Syngenta Participations AG Process for the preparation of benzonorbornane derivatives
TWI396676B (en) * 2005-12-12 2013-05-21 Syngenta Participations Ag Process for the preparation of amines
EP2213167A1 (en) 2006-01-16 2010-08-04 Syngenta Participations AG Anthranilamide derivatives and their use for the control of insects and acari
KR101444680B1 (en) * 2006-04-06 2014-10-02 신젠타 파티서페이션즈 아게 Fungicidal compositions
JP2009532403A (en) * 2006-04-06 2009-09-10 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト Fungicidal composition
WO2007115765A1 (en) * 2006-04-06 2007-10-18 Syngenta Participations Ag Fungicidal compositions
US20090221588A1 (en) * 2006-04-06 2009-09-03 Syngenta Crop Protection, Inc. Fungicidal compositions
JP2009532402A (en) * 2006-04-06 2009-09-10 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト Fungicidal composition
AU2007234870B2 (en) * 2006-04-07 2013-07-04 Syngenta Participations Ag Method of controlling phytopathogenic diseases on turfgrass
JP2009536614A (en) * 2006-04-07 2009-10-15 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト Methods for controlling phytopathogenic diseases related to turfgrass
WO2007118069A3 (en) * 2006-04-07 2008-11-06 Syngenta Participations Ag Method of controlling phytopathogenic diseases on turfgrass
TWI458431B (en) * 2006-04-07 2014-11-01 Syngenta Participations Ag Method of controlling phytopathogenic diseases on turfgrass
KR101419277B1 (en) * 2006-04-07 2014-07-16 신젠타 파티서페이션즈 아게 Method of controlling phytopathogenic diseases on turfgrass
WO2007124907A3 (en) * 2006-04-27 2008-01-10 Syngenta Participations Ag Heterocyclyl-carboxylic acid (benzonorbornene-5-yl)amide derivatives as fungicides for agrochemical use
WO2007124907A2 (en) * 2006-04-27 2007-11-08 Syngenta Participations Ag Heterocyclyl-carboxylic acid (benzonorbornene-5-yl)amide derivatives as fungicides for agrochemical use
WO2008009405A2 (en) 2006-07-17 2008-01-24 Syngenta Participations Ag Novel pyridazine derivatives
WO2008017443A1 (en) * 2006-08-08 2008-02-14 Syngenta Participations Ag Process for the production of aromatic amines in the presence of a palladium complex comprising a ferrocenyl biphosphine ligand
WO2008049584A1 (en) 2006-10-25 2008-05-02 Syngenta Participations Ag Novel pyridazine derivatives
WO2008098928A3 (en) * 2007-02-14 2009-08-27 Basf Se Method of inducing virus tolerance of plants
WO2008098928A2 (en) * 2007-02-14 2008-08-21 Basf Se Method of inducing virus tolerance of plants
WO2008113447A3 (en) * 2007-03-16 2009-08-13 Syngenta Ltd Novel solid forms of a microbiocide
AU2008228561B2 (en) * 2007-03-16 2013-01-17 Syngenta Limited Novel solid forms of a microbiocide
US8580835B2 (en) 2007-03-16 2013-11-12 Syngenta Crop Protection, Llc Solid forms of a microbiocide
WO2008113447A2 (en) 2007-03-16 2008-09-25 Syngenta Limited Novel solid forms of a microbiocide
EP2679093A1 (en) 2007-03-16 2014-01-01 Syngenta Participations AG. Novel solid forms of a microbiocide
EP2193716A1 (en) 2007-04-25 2010-06-09 Syngenta Participations AG Fungicidal Compositions
AU2013201960B2 (en) * 2007-04-25 2013-08-01 Syngenta Participations Ag Fungicidal compositions
AU2013201942B2 (en) * 2007-04-25 2013-08-01 Syngenta Participations Ag Fungicidal compositions
EP2196089A1 (en) 2007-04-25 2010-06-16 Sygenta Participations AG. Fungicidal Compositions
EP2229814A1 (en) 2007-04-25 2010-09-22 Syngenta Participations AG. Fungicidal Compositions
US9314022B2 (en) 2007-04-25 2016-04-19 Syngenta Crop Protection, Llc Fungicidal compositions
EP2201839A1 (en) 2007-04-25 2010-06-30 Syngenta Participations AG Fungicidal compositions
EA017077B1 (en) * 2007-04-25 2012-09-28 Синджента Партисипейшнс Аг Fungicidal compositions
KR101530867B1 (en) * 2007-04-25 2015-06-23 신젠타 파티서페이션즈 아게 Fungicidal compositions
AU2013201953B2 (en) * 2007-04-25 2013-08-01 Syngenta Participations Ag Fungicidal compositions
US11647749B2 (en) 2007-04-25 2023-05-16 Syngenta Participations Ag Fungicidal compositions
WO2008131901A1 (en) 2007-04-25 2008-11-06 Syngenta Participations Ag Fungicidal compositions
AU2013201955B2 (en) * 2007-04-25 2013-08-01 Syngenta Participations Ag Fungicidal compositions
AU2013201951B2 (en) * 2007-04-25 2013-08-01 Syngenta Participations Ag Fungicidal compositions
EP2206431A1 (en) 2007-04-25 2010-07-14 Sygenta Participations AG. Fungicidal Compositions
TWI424814B (en) * 2007-04-25 2014-02-01 Syngenta Participations Ag Fungicidal compositions
EP2204093A1 (en) 2007-04-25 2010-07-07 Sygenta Participations AG. Fungicidal Compositions
CN102726409B (en) * 2007-04-25 2014-08-13 先正达参股股份有限公司 Fungicidal compositions
CN102726405A (en) * 2007-04-25 2012-10-17 先正达参股股份有限公司 Fungicidal compositions
CN102726405B (en) * 2007-04-25 2014-07-02 先正达参股股份有限公司 Fungicidal compositions
AU2013201962B2 (en) * 2007-04-25 2013-08-01 Syngenta Participations Ag Fungicidal compositions
AU2013201958B2 (en) * 2007-04-25 2013-08-01 Syngenta Participations Ag Fungicidal compositions
AU2013201947B2 (en) * 2007-04-25 2013-08-01 Syngenta Participations Ag Fungicidal compositions
AU2013201946B2 (en) * 2007-04-25 2013-08-01 Syngenta Participations Ag Fungicidal compositions
EP2196088A1 (en) 2007-04-25 2010-06-16 Syngenta Participations AG Fungicidal Compositions
EP2193715A1 (en) 2007-04-25 2010-06-09 Sygenta Participations AG. Fungicidal Compositions
US10143201B2 (en) 2007-04-25 2018-12-04 Syngenta Crop Protection, Llc Fungicidal compositions
US8551912B2 (en) 2007-04-25 2013-10-08 Syngenta Crop Protection Llc Fungicidal compositions
EP2193714A1 (en) 2007-04-25 2010-06-09 Sygenta Participations AG. Fungicidal Compositions
US9642365B2 (en) 2007-04-25 2017-05-09 Syngenta Crop Protection, Llc Fungicidal compositions
EP2193717A1 (en) 2007-04-25 2010-06-09 Sygenta Participations AG. Fungicidal Compositions
AU2013201961B2 (en) * 2007-04-25 2013-08-01 Syngenta Participations Ag Fungicidal compositions
WO2009010260A2 (en) 2007-07-16 2009-01-22 Syngenta Participations Ag Condensed anthranilamide insecticides
WO2009024341A2 (en) 2007-08-22 2009-02-26 Syngenta Participations Ag, Condensed anthran i lami de derivatives as insectisides
EP3510869A1 (en) 2007-09-20 2019-07-17 Bayer Cropscience LP Combinations comprising a fungicidal strain and an active compound
EP2614716A1 (en) 2007-09-20 2013-07-17 Basf Se Combinations comprising a fungicidal strain and at least one additional fungicide
EP2614713A1 (en) 2007-09-20 2013-07-17 Basf Se Combinations comprising a fungicidal strain and at least one additional fungicide
EP2319319A1 (en) 2007-09-20 2011-05-11 Basf Se Combinations comprising a fungicidal strain and at least one additional fungicide
EP2614717A1 (en) 2007-09-20 2013-07-17 Basf Se Combinations comprising a fungicidal strain and at least one additional fungicide
EP2614714A1 (en) 2007-09-20 2013-07-17 Basf Se Combinations comprising a fungicidal strain and at least one additional fungicide
EP2614712A1 (en) 2007-09-20 2013-07-17 Basf Se Combinations comprising a fungicidal strain and at least one additional fungicide
US9078447B2 (en) 2007-09-20 2015-07-14 Bayer Cropscience Lp Combinations comprising a fungicidal strain and an active compound
EP2614715A1 (en) 2007-09-20 2013-07-17 Basf Se Combinations comprising a fungicidal strain and at least one additional fungicide
WO2009053101A1 (en) 2007-10-26 2009-04-30 Syngenta Participations Ag Novel imidazole derivatives
EP2053044A1 (en) 2007-10-26 2009-04-29 Syngenta Participations AG Novel imidazole derivatives
WO2009053102A1 (en) 2007-10-26 2009-04-30 Syngenta Participations Ag Novel imidazole derivatives
EP2053045A1 (en) 2007-10-26 2009-04-29 Syngenta Participations AG Novel imidazole derivatives
EP2053046A1 (en) 2007-10-26 2009-04-29 Syngeta Participations AG Novel imidazole derivatives
WO2009090039A1 (en) 2008-01-16 2009-07-23 Syngenta Participations Ag Pyridazine fungicides
EP3586631A2 (en) 2008-02-05 2020-01-01 Basf Se Plant health composition
US20110178310A1 (en) * 2008-05-14 2011-07-21 Syngenta Crop Protection, Inc. Process for the preparation of amides
US20120289707A1 (en) * 2008-05-14 2012-11-15 Syngenta Crop Protection, Llc Process for the preparation of amides
US8227619B2 (en) * 2008-05-14 2012-07-24 Syngenta Limited Process for the preparation of amides
US8871679B2 (en) 2008-07-04 2014-10-28 Basf Se Fungicidal mixtures comprising substituted 1-methylpyrazol-4-ylcarboxanilides
WO2010072632A1 (en) 2008-12-24 2010-07-01 Syngenta Limited Methods for the preparation of aryl amides
WO2010086103A2 (en) 2009-01-30 2010-08-05 Bayer Cropscience Aktiengesellschaft Use of succinate dehydrogenase inhibitors for controlling powdery mildew primary infections
US8822506B2 (en) 2009-01-30 2014-09-02 Bayer Cropscience Ag Use of succinate dehydrogenase inhibitors for controlling powdery mildew primary infections
AU2010207788B2 (en) * 2009-01-30 2015-08-20 Bayer Cropscience Aktiengesellschaft Use of succinate dehydrogenase inhibitors for controlling powdery mildew primary infections
WO2010086103A3 (en) * 2009-01-30 2011-04-21 Bayer Cropscience Aktiengesellschaft Use of succinate dehydrogenase inhibitors for controlling powdery mildew primary infections
WO2010091803A2 (en) 2009-02-13 2010-08-19 Bayer Cropscience Ag Use of succinate dehydrogenase inhibitors for extending shelf life of fruits and vegetables
US11241010B2 (en) 2009-02-13 2022-02-08 Bayer Intellectual Property Gmbh Use of succinate dehydrogenase inhibitors for extending shelf life of fruits and vegetables
US10548315B2 (en) 2009-02-13 2020-02-04 Bayer Intellectual Property Gmbh Use of succinate dehydrogenase inhibitors for extending shelf life of fruits and vegetables
WO2010100008A2 (en) 2009-03-06 2010-09-10 Syngenta Participations Ag Fungicidal compositions
WO2010102866A1 (en) 2009-03-12 2010-09-16 Syngenta Participations Ag Imidazole derivatives
US9012360B2 (en) 2009-03-25 2015-04-21 Bayer Intellectual Property Gmbh Synergistic combinations of active ingredients
WO2010130532A1 (en) 2009-05-15 2010-11-18 Syngenta Limited Process for purification of 1-methylpyrazole-4-carboxylic acid esters
JP2012526740A (en) * 2009-05-15 2012-11-01 シンジェンタ リミテッド Process for purification of 1-methylpyrazole-4-carboxylic acid ester
EP2255626A1 (en) 2009-05-27 2010-12-01 Bayer CropScience AG Use of succinate dehydrogenase inhibitors to increase resistance of plants or parts of plants to abiotic stress
US9877482B2 (en) 2009-06-02 2018-01-30 Bayer Intellectual Property Gmbh Use of succinate dehydrogenase inhibitors for controlling Sclerotinia ssp
US9232794B2 (en) 2009-06-02 2016-01-12 Bayer Intellectual Property Gmbh Use of succinate dehydrogenase inhibitors for controlling Sclerotinia ssp
WO2011006603A2 (en) 2009-07-16 2011-01-20 Bayer Cropscience Ag Synergistic active substance combinations containing phenyl triazoles
WO2011012618A2 (en) 2009-07-28 2011-02-03 Syngenta Participations Ag Processes relating to the alkylation of pyrazoles
WO2011012620A2 (en) 2009-07-31 2011-02-03 Syngenta Participations Ag Processes for the alkylation of pyrazoles
CN102574779A (en) * 2009-08-06 2012-07-11 先正达参股股份有限公司 Process for the preparation of pyrazole carboxylic acid amides
CN102574779B (en) * 2009-08-06 2014-10-15 先正达参股股份有限公司 Process for the preparation of pyrazole carboxylic acid amides
WO2011015416A1 (en) * 2009-08-06 2011-02-10 Syngenta Participations Ag Process for the preparation of pyrazole carboxylic acid amides
AU2010280923B2 (en) * 2009-08-06 2014-08-07 Syngenta Participations Ag Process for the preparation of pyrazole carboxylic acid amides
US8507694B2 (en) 2009-08-06 2013-08-13 Syngenta Crop Protection Llc Process for the preparation of pyrazole carboxylic acid amides
EA019475B1 (en) * 2009-08-06 2014-03-31 Зингента Партисипейшнс Аг Process for the preparation of pyrazole carboxylic acid amides
WO2011032657A2 (en) 2009-09-16 2011-03-24 Bayer Cropscience Ag Use of succinate dehydrogenase inhibitors for increasing the content of desired ingredients in crops
EP2301350A1 (en) 2009-09-16 2011-03-30 Bayer CropScience AG Use of succinate dehydrogenase inhibitors for increasing the content of desired ingredients in crops
WO2011069893A1 (en) 2009-12-08 2011-06-16 Basf Se Pesticidal mixtures
US9585391B2 (en) 2009-12-08 2017-03-07 Basf Se Pesticidal mixtures
US8748342B2 (en) 2009-12-08 2014-06-10 Basf Se Pesticidal mixtures
WO2011069890A2 (en) 2009-12-08 2011-06-16 Basf Se Pesticidal mixtures
US9049859B2 (en) 2009-12-08 2015-06-09 Basf Se Pesticidal mixtures
WO2011076501A1 (en) 2009-12-22 2011-06-30 Syngenta Participations Ag Novel 5-(pyridin-3-yl)-pyridanize derivatives and their use as microbicides
EP3150069A1 (en) 2009-12-22 2017-04-05 Mitsui Chemicals Agro, Inc. Plant disease control composition and method for controlling plant disease by applying the same
WO2011082913A1 (en) 2010-01-08 2011-07-14 Syngenta Participations Ag Fungicidal compositions containing isopyrazam, azoxystrobin and cyproconazole
WO2011095461A1 (en) 2010-02-04 2011-08-11 Syngenta Participations Ag Pyridazine derivatives, processes for their preparation and their use as fungicides
WO2011095459A1 (en) 2010-02-04 2011-08-11 Syngenta Participations Ag Pyridazine derivatives, process for their preparation and their use as fungicides
WO2011095496A2 (en) 2010-02-05 2011-08-11 Bayer Cropscience Ag Use of succinate dehydrogenase (sdh) inhibitors in treating plant species of the family of true grasses
EP2353387A1 (en) 2010-02-05 2011-08-10 Bayer CropScience AG Use of succinate dehydrogenase (SDH) inhibitors in the treatment of plant types in the sweet grass family
US9215872B2 (en) 2010-02-05 2015-12-22 Bayer Intellectual Property Gmbh Use of succinate dehydrogenase (SDH) inhibitors in the treatment of plant species from the family of the true grasses
US10820592B2 (en) * 2010-02-05 2020-11-03 Rotam Agrochem International Co., Ltd. Method for treating fungal infections, fungicidal compositions and their use
US20120302559A1 (en) * 2010-02-05 2012-11-29 Rotam Agrochem International Co., Ltd. Method for treating fungal infections, fungicidal compositions and their use
WO2011104183A1 (en) 2010-02-24 2011-09-01 Syngenta Participations Ag Novel microbicides
WO2011113789A1 (en) 2010-03-15 2011-09-22 Syngenta Participations Ag Process for preparing alkyl 2-alkoxymethylene-4,4-difluoro-3-oxobutyrates
WO2011113788A1 (en) 2010-03-15 2011-09-22 Syngenta Participations Ag Process for purifying 3-difluoromethyl-1-methyl-1h-pyrazole-4-carboxylic acid
EP2377397A1 (en) 2010-04-14 2011-10-19 Bayer CropScience AG Use of fungicidal agents for controlling mycoses in palm trees
WO2011128262A2 (en) 2010-04-14 2011-10-20 Bayer Cropscience Ag Use of fungicidal agents for controlling mycoses on palms
WO2011147953A1 (en) 2010-05-28 2011-12-01 Basf Se Pesticidal mixtures
US8859558B2 (en) 2010-06-07 2014-10-14 Dow Agrosciences, Llc. Pyrazinyl carboxamides as fungicides
WO2012001040A1 (en) 2010-07-02 2012-01-05 Syngenta Participations Ag Novel microbiocidal dioxime ether derivatives
US9788540B2 (en) 2010-07-26 2017-10-17 Bayer Intellectual Property Gmbh Use of succinate dehydrogenase inhibitors and/or respiratory chain complex III inhibitors for improving the ratio of harmful to beneficial microorganisms
WO2012013590A2 (en) 2010-07-26 2012-02-02 Bayer Cropscience Ag Use of succinate dehydrogenase inhibitors and/or respiratory chain complex iii inhibitors for improving the ratio of harmful to beneficial microorganisms
US20160000067A1 (en) * 2010-07-27 2016-01-07 Syngenta Limited Formulations
US9807999B2 (en) * 2010-07-27 2017-11-07 Syngenta Limited Formulations
WO2012013754A1 (en) 2010-07-29 2012-02-02 Syngenta Participations Ag Novel microbiocidal dioxime ether derivatives
WO2012019950A1 (en) 2010-08-10 2012-02-16 Syngenta Participations Ag Process for the preparation of 3-haloalkylpyrazoles
WO2012020776A1 (en) 2010-08-10 2012-02-16 住友化学株式会社 Plant disease control composition and application for same
WO2012041874A1 (en) 2010-10-01 2012-04-05 Syngenta Participations Ag Fungicidal compositions
EP3175712A1 (en) 2010-10-01 2017-06-07 Syngenta Participations Ag Fungicidal compositions
WO2012052544A1 (en) 2010-10-21 2012-04-26 Syngenta Limited Agrochemical concentrates containing isopyrazam
WO2012055864A1 (en) 2010-10-27 2012-05-03 Solvay Sa Process for the preparation of pyrazole-4-carboxamides
US8987470B2 (en) 2010-10-27 2015-03-24 Solvay Sa Process for the preparation of pyrazole-4-carboxamides
US9375004B2 (en) 2010-11-15 2016-06-28 Bayer Intellectual Property Gmbh 5-halogenopyrazolecarboxamides
WO2012065932A1 (en) 2010-11-15 2012-05-24 Bayer Cropscience Ag Decahydro-1,4-methanonaphthalen carboxamides
WO2012065947A1 (en) 2010-11-15 2012-05-24 Bayer Cropscience Ag 5-halogenopyrazolecarboxamides
WO2012065945A1 (en) 2010-11-15 2012-05-24 Bayer Cropscience Ag 5-halogenopyrazole(thio)carboxamides
WO2012066122A1 (en) 2010-11-18 2012-05-24 Syngenta Participations Ag 2 - (pyridin- 2 -yl) -quinazoline derivatives and their use as microbicides
WO2012069652A2 (en) 2010-11-26 2012-05-31 Syngenta Participations Ag Fungicide mixtures
WO2012110464A1 (en) 2011-02-17 2012-08-23 Bayer Cropscience Ag Use of sdhi fungicides on conventionally bred asr-tolerant, stem canker resistant and/or frog-eye leaf spot resistant soybean varieties
WO2012175511A1 (en) 2011-06-21 2012-12-27 Bayer Intellectual Property Gmbh Method for producing pyrazolylcarboxanilides
WO2013011010A1 (en) 2011-07-19 2013-01-24 Syngenta Participations Ag Fungizide mixtures
WO2013026866A2 (en) 2011-08-23 2013-02-28 Syngenta Participations Ag Novel microbiocides
US9204646B2 (en) 2012-05-09 2015-12-08 Bayer Cropscience Ag Pyrazole tetrahydronaphthyl carboxamides
WO2013167548A1 (en) * 2012-05-09 2013-11-14 Bayer Cropscience Ag Pyrazole tetrahydronaphthyl carboxamides
US9688608B2 (en) 2012-05-09 2017-06-27 Bayer Cropscience Ag Pyrazole tetrahydronaphthyl carboxamides
EP2662364A1 (en) * 2012-05-09 2013-11-13 Bayer CropScience AG Pyrazole tetrahydronaphthyl carboxamides
WO2014060177A1 (en) 2012-10-16 2014-04-24 Syngenta Participations Ag Fungicidal compositions
EP3042562A1 (en) 2012-11-19 2016-07-13 Arch Wood Protection, Inc. Succinate dehydrogenase inhibitor containing compositions
WO2014078849A1 (en) 2012-11-19 2014-05-22 Lonza, Inc. Succinate dehydrogenase inhibitor containing compositions
WO2014083088A2 (en) 2012-11-30 2014-06-05 Bayer Cropscience Ag Binary fungicidal mixtures
WO2014095826A1 (en) 2012-12-18 2014-06-26 Bayer Cropscience Ag Binary fungicidal and bactericidal combinations
WO2014095678A1 (en) * 2012-12-19 2014-06-26 Bayer Cropscience Ag Tetrahydronaphthyl(thio) carboxamides
US9630943B2 (en) 2012-12-19 2017-04-25 Bayer Cropscience Ag Tetrahydronaphthyl(thio) carboxamides
WO2014095677A1 (en) * 2012-12-19 2014-06-26 Bayer Cropscience Ag Difluoromethyl-nicotinic- tetrahydronaphtyl carboxamides
CN104870426A (en) * 2012-12-19 2015-08-26 拜耳作物科学股份公司 Tetrahydronaphthyl(Thio) Carboxamides
US9428459B2 (en) 2012-12-19 2016-08-30 Bayer Cropscience Ag Difluoromethyl-nicotinic- tetrahydronaphtyl carboxamides
EP2980078A1 (en) 2014-07-29 2016-02-03 Solvay SA Process for the preparation of pyrazole-4-carboxamides
US10829456B2 (en) 2016-01-28 2020-11-10 Solvay Sa Halogen substituted diketones, pyrazole compounds and processes for the manufacture of pyrazole compounds
WO2017129759A1 (en) 2016-01-28 2017-08-03 Solvay Sa Halogen substituted diketones, pyrazole compounds and processes for the manufacture of pyrazole compounds
WO2017194517A1 (en) 2016-05-10 2017-11-16 Solvay Sa Composition comprising 3-(haloalkyl or formyl)-1h-pyrazole-4-carboxylic acids or esters, its manufacture and its use for the preparation of carboxamides
WO2018024644A1 (en) 2016-08-02 2018-02-08 Solvay Sa Manufacture of hydrazinyl compounds useful in the manufacture of pyrazole carboxylic acid and derivatives, hydrazinyl compounds and their use
WO2018083281A1 (en) 2016-11-07 2018-05-11 Solvay Sa Process for the manufacture of carboxylic acids or carboxylic acid derivatives
WO2018202677A1 (en) 2017-05-02 2018-11-08 Solvay Sa Process for the manufacture of carboxylic acids or carboxylic acid derivatives
US11560384B2 (en) 2017-05-04 2023-01-24 University Of Utah Research Foundation Benzonorbornadiene derivatives and reactions thereof
US11491133B2 (en) 2017-08-02 2022-11-08 Sunovion Pharmaceuticals Inc. Heteroaryl-isochroman compounds and uses thereof
WO2019110795A1 (en) 2017-12-08 2019-06-13 Solvay Sa Oxidation of a pyrazolyl ketone compound to the corresponding carboxylic acid
EP3495351A1 (en) 2017-12-08 2019-06-12 Solvay Sa Oxidation of a pyrazolyl ketone compound to the corresponding carboxylic acid
WO2019122204A1 (en) 2017-12-22 2019-06-27 Solvay Sa Process for the manufacture of pyrazole compounds
WO2019122194A1 (en) 2017-12-22 2019-06-27 Solvay Sa Process for the manufacture of iminium compounds and their application in the manufacture of pyrazole derivatives
WO2019122164A1 (en) 2017-12-22 2019-06-27 Solvay Sa Process for the manufacture of pyrazole carboxylic derivatives and precursors thereof
WO2021138315A1 (en) * 2020-01-03 2021-07-08 Blue Oak Pharmaceuticals, Inc. Compounds and compositions for treating cns disorders

Also Published As

Publication number Publication date
TW200412847A (en) 2004-08-01
JP2006511485A (en) 2006-04-06
US7994093B2 (en) 2011-08-09
CA2498851C (en) 2011-04-19
RS20050297A (en) 2007-08-03
KR100858013B1 (en) 2008-09-11
CN1705668A (en) 2005-12-07
SI1556385T1 (en) 2010-07-30
EG24050A (en) 2008-04-13
AU2003280376B2 (en) 2010-03-11
FR18C1024I1 (en) 2018-07-13
AU2003280376A1 (en) 2004-05-04
CN100448876C (en) 2009-01-07
RS51937B (en) 2012-02-29
AR041649A1 (en) 2005-05-26
MXPA05003899A (en) 2005-06-22
BR0314875B1 (en) 2014-11-18
NO20052201L (en) 2005-05-27
EA200500574A1 (en) 2005-10-27
CR7727A (en) 2008-02-12
MEP31608A (en) 2010-10-10
CA2498851A1 (en) 2004-04-29
IL190341A0 (en) 2009-09-22
ES2342714T3 (en) 2010-07-13
BR0314875A (en) 2005-08-02
JP4607591B2 (en) 2011-01-05
MA27405A1 (en) 2005-06-01
EA015708B1 (en) 2011-10-31
PL376574A1 (en) 2006-01-09
UA81784C2 (en) 2008-02-11
GB0224316D0 (en) 2002-11-27
US20100010063A1 (en) 2010-01-14
NO331404B1 (en) 2011-12-19
ATE460418T1 (en) 2010-03-15
US20080051446A1 (en) 2008-02-28
GEP20084500B (en) 2008-10-10
US7598395B2 (en) 2009-10-06
ME00223B (en) 2011-02-10
ZA200501870B (en) 2006-02-22
KR100872010B1 (en) 2008-12-05
EP1556385B1 (en) 2010-03-10
CY1110077T1 (en) 2015-01-14
IL167290A (en) 2010-04-15
HK1082254A1 (en) 2006-06-02
IL190341A (en) 2012-04-30
TWI319704B (en) 2010-01-21
PL221973B1 (en) 2016-06-30
HRP20050441A2 (en) 2006-09-30
KR20050055767A (en) 2005-06-13
KR20080025767A (en) 2008-03-21
TNSN05112A1 (en) 2007-05-14
BE2013C039I2 (en) 2023-03-07
FR18C1024I2 (en) 2019-05-17
ECSP055675A (en) 2005-07-06
NZ539376A (en) 2007-05-31
EA010264B1 (en) 2008-06-30
DE60331670D1 (en) 2010-04-22
GEP20115347B (en) 2011-12-12
HRP20050441B1 (en) 2014-04-11
EP1556385A1 (en) 2005-07-27
DK1556385T3 (en) 2010-06-14
PT1556385E (en) 2010-06-14
EA200800883A1 (en) 2008-12-30

Similar Documents

Publication Publication Date Title
EP1556385B1 (en) Heterocyclocarboxamide derivatives
US7956194B2 (en) Microbiocidal (E.G. fungicidal) 1,2,3-triazole derivatives
US20040138265A1 (en) Carboxamides as fungicides in agriculture
CA2817717A1 (en) Decahydro-1,4-methanonaphthalen carboxamides
EP1360176B1 (en) Pyrrolecarboxamides for use as fungicides
AU2002250905A1 (en) Pyrrolecarboxamides for the use as fungicides
AU2002225039A1 (en) Carboxamides as fungicides in agriculture

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: P-2005/0297

Country of ref document: YU

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2005/01870

Country of ref document: ZA

Ref document number: 200501870

Country of ref document: ZA

Ref document number: 2003280376

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 167290

Country of ref document: IL

WWE Wipo information: entry into national phase

Ref document number: 2498851

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2003772217

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 1-2005-500546

Country of ref document: PH

WWE Wipo information: entry into national phase

Ref document number: 05025159

Country of ref document: CO

WWE Wipo information: entry into national phase

Ref document number: KE

WWE Wipo information: entry into national phase

Ref document number: 10530737

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 539376

Country of ref document: NZ

Ref document number: PA/a/2005/003899

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 2004544232

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 1020057006640

Country of ref document: KR

Ref document number: 638/CHENP/2005

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: 20038A16261

Country of ref document: CN

Ref document number: 376574

Country of ref document: PL

WWE Wipo information: entry into national phase

Ref document number: 200500574

Country of ref document: EA

WWE Wipo information: entry into national phase

Ref document number: DZP2005000168

Country of ref document: DZ

WWE Wipo information: entry into national phase

Ref document number: P20050441A

Country of ref document: HR

WWE Wipo information: entry into national phase

Ref document number: 8803

Country of ref document: GE

Ref document number: 1200500672

Country of ref document: VN

WWP Wipo information: published in national office

Ref document number: 1020057006640

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 2003772217

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 10254

Country of ref document: GE

WWP Wipo information: published in national office

Ref document number: 10530737

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 190341

Country of ref document: IL