WO2012038521A1 - Novel microbiocides - Google Patents

Novel microbiocides Download PDF

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Publication number
WO2012038521A1
WO2012038521A1 PCT/EP2011/066553 EP2011066553W WO2012038521A1 WO 2012038521 A1 WO2012038521 A1 WO 2012038521A1 EP 2011066553 W EP2011066553 W EP 2011066553W WO 2012038521 A1 WO2012038521 A1 WO 2012038521A1
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Prior art keywords
alkyl
halogen
phenyl
optionally substituted
independently selected
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PCT/EP2011/066553
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French (fr)
Inventor
Werner Zambach
Daniel Stierli
Kurt Nebel
Andrea Bortolato
Clara Massol-Frieh
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Syngenta Participations Ag
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Priority to CN2011800456131A priority Critical patent/CN103124723A/en
Priority to BR112013006671A priority patent/BR112013006671A2/en
Priority to EP11761353.9A priority patent/EP2619181A1/en
Priority to US13/825,808 priority patent/US20140309244A1/en
Publication of WO2012038521A1 publication Critical patent/WO2012038521A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, 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
    • A01N43/42—Biocides, 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 condensed with carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
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    • C07D213/02—Heterocyclic 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
    • C07D213/04—Heterocyclic 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
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    • C07D213/02—Heterocyclic 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
    • C07D213/04—Heterocyclic 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
    • C07D213/60—Heterocyclic 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
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    • C07D213/04—Heterocyclic 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
    • C07D213/60—Heterocyclic 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
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    • C07D213/04—Heterocyclic 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
    • C07D213/60—Heterocyclic 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
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/65—One oxygen atom attached in position 3 or 5
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    • C07D213/02—Heterocyclic 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
    • C07D213/04—Heterocyclic 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
    • C07D213/60—Heterocyclic 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
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    • C07D213/00—Heterocyclic 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
    • C07D213/02—Heterocyclic 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
    • C07D213/04—Heterocyclic 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
    • C07D213/60—Heterocyclic 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/80—Acids; Esters in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07D213/00—Heterocyclic 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
    • C07D213/02—Heterocyclic 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
    • C07D213/04—Heterocyclic 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
    • C07D213/60—Heterocyclic 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/84—Nitriles
    • C—CHEMISTRY; METALLURGY
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    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic 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
    • C07D495/04—Ortho-condensed systems

Definitions

  • the present invention relates to novel microbiocidally active, in particular fungicidally active, oxime derivatives. It further relates to intermediates used in the preparation of these compounds, to compositions which comprise these compounds and to their use in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.
  • Fungicidally active bisoximes are described in WO08074418.
  • the present invention accordingly relates to bisoxime derivatives of formula (I)
  • R 1 represents hydrogen, halogen, CN, SH, Ci-C 8 alkylthio, Ci-C 8 alkylsulphinyl, Ci-C 8 alkylsulphonyl, NH 2 , Ci-Cio alkyl, C 3 -C 8 cycloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl,
  • R 8 0 carbonyl(Ci-C 4 alkyl), phenyl or pyridyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , NH-C r C 8 alkyl, N(C r C 8 alkyl) 2 , N0 2 , OR 8 , C r C alkyl, C r C haloalkyl, C 3 -C 6 cycloalkyl and a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms;
  • R 2 represents hydrogen, Ci-C 8 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, benzyl, phenyl or pyridyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , N0 2 , OH, C r C alkyl, C r C haloalkyl, C r C alkoxy and C r C haloalkoxy;
  • D 1 represents N or C-Y 1 ;
  • D 2 represents N or C-Y 2 ;
  • A represents group A-l, A-2, or A-3:
  • a 1 represents the cycle A la , A l , or A lc :
  • R 3 represents hydrogen, halogen, CN, SH, Ci-C 8 alkylthio, Ci-C 8 alkylsulphinyl, Ci-C 8 alkylsulphonyl, NH 2 , Ci-Cio alkyl, C 3 -C 8 cycloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl,
  • R 8 0 carbonyl(Ci-C 4 alkyl), phenyl or pyridyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , NH-C r C 8 alkyl, N(C r C 8 alkyl) 2 , N0 2 , OR 8 , d-C alkyl, d-C haloalkyl, C 3 -C 6 cycloalkyl and a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms;
  • R 4 , R 5 , R 6 and R 7 independently of one another represent hydrogen, halogen, CN, N0 2 , Ci-C 8 alkyl, C 3 -C 8 cycloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, phenyl, a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, COR 9 , OR 8 , SH, Ci-C 8 -alkylthio, Ci-C 8 - alkylsulphinyl, Ci-C 8 -alkylsulphonyl, phenylthio, phenylsulphinyl, phenylsulphonyl, N(R 10 ) 2 , C0 2 R 8 , 0(CO)R 9 , CON(R 10 )
  • R 5 and R 6 , R 6 and R 4 , or R 7 and R 4 together with the fragment of the ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a partially or fully unsaturated 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from O, S, N and N(R 10 ), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, and wherein the ring formed by R 5 and R 6 , R 6 and R 4 , or R 7 and R 4 is optionally substituted by one or more groups independently selected from halogen, CN,
  • G 1 and G 2 independently of one another represent -C(R 12 R 13 )-;
  • G 3 represents -C(R 12 R 13 )-, O, N(R 14 ) or S;
  • each R 12 and R 13 independently of one another represent hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyi, C1-C4 alkoxy or C1-C4 haloalkoxy;
  • R 14 represents hydrogen, OH, C1-C4 alkyl, d-d alkoxy, C 3 -C 6 cycloalkyl, C d alkylcarbonyl or Ci-C 8 haloalkylcarbonyl;
  • p 0, 1 or 2;
  • X represents X-2, X-3, X-4 or X-5:
  • each R 15 and R 16 independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl, d-d haloalkyi or phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, Crd alkyl, d-d haloalkyi, Crd alkoxy and Crd haloalkoxy;
  • R 15 and R 16 together with the carbon atom to which they are attached may form a
  • each R 17 and R 18 independently of one another represent hydrogen, halogen, Crd alkyl or -d haloalkyi;
  • each R 19 , R 20 , R 21 and R 22 independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl, C1-C4 haloalkyi or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, d-d alkyl, d- haloalkyi, C d alkoxy and Crd haloalkoxy;
  • R 19 and R 20 together with the carbon atom to which they are attached may form a C 3 -C 6 cycloalkyl group or a C 3 -C 6 halocycloalkyl group;
  • radicals Z 1 , Z 3 , Z 6 and Z 10 are not substituted by OH; and wherein none of Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 , Z 7 , Z 8 , Z 9 , Z 10 , Z 11 , Z 12 , Z 13 and Z 14 represent a carbon atom substituted by two OH;
  • Y 1 , Y 2 and Y 3 independently of one another represent hydrogen, halogen, CN, N0 2 , Ci-Cs alkyl, C 3 -C 8 cycloalkyi, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, phenyl, a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, COR 9 , OR 8 , SH, Ci-C 8 -alkylthio, d-C 8 - alkylsulphinyl, Ci-C 8 -alkylsulphonyl, phenylthio, phenylsulphinyl, phenylsulphonyl, N(R 10 ) 2 , C0 2 R 8 , 0(CO)R 9 , CON(R 10 )
  • each R 8 independently of one another represents hydrogen, d-C 8 alkyl, C 3 -C 8 cycloalkyi, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl, benzyl or a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl, benzyl and heterocycle are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , N0 2 , OH, C r C alkyl, C r C -haloalkyl, C r C alkoxy, C r C haloalkoxy, and Crd-alkoxy-Crd-alkyl;
  • each R 9 independently of one another represents hydrogen, d-C 8 alkyl, C 3 -C 8 cycloalkyi, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, phenyl, benzyl or pyridyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , N0 2 , OH, Crd alkyl, Crd haloalkyl, Crd alkoxy and d-C 4 haloalkoxy;
  • each R 10 independently of one another represents hydrogen, OH, d-C 8 alkyl, d-C 8 alkoxy, CrC 8 -alkoxy-CrC 4 -alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, or COR 9 , wherein the alkyl, alkoxy, alkenyl and alkynyl are optionally substituted by one or more halogen; wherein when two radicals R are attached to the same nitrogen atom, these radicals can be identical or different;
  • cycle formed is optionally substituted by one or more groups
  • halogen independently selected from halogen, CN, NH 2 , N0 2 , OH, d-d alkyl, d-d haloalkyi, d-d alkoxy and d-d haloalkoxy;
  • the invention covers all agronomically acceptable salts, isomers, structural isomers, stereoisomers, diastereoisomers, enantiomers, tautomers, atropisomers and N-oxides of those compounds.
  • the compounds of formula I may exist in different geometric or optical isomeric forms or in different tautomeric forms. One or more centres of chirality may be present, in which case compounds of the formula I may be present as pure enantiomers, mixtures of enantiomers, pure diastereomers or mixtures of diastereomers.
  • This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds. Also
  • Atropisomerism may occur as a result of a restricted rotation about a single bond.
  • Halogen either as a lone substituent or in combination with another substituent (e.g. haloalkyi) is generally fluorine, chlorine, bromine or iodine, and usually fluorine, chlorine or bromine.
  • Each alkyl moiety (including the alkyl moiety of alkoxy, alkylthio, etc.) is a straight or branched chain and, depending on the number of carbon atoms it contains, is, for example, methyl, ethyl, ⁇ propyl, -butyl, 7-pentyl, ⁇ -hexyl, /so-propyl, sec-butyl, /so-butyl, te i-butyl, 7eopentyl, -heptyl or 1,3-dimethylbutyl, and usually methyl or ethyl.
  • the alkenyl and alkynyl groups can be mono- or di -unsaturated and are examples thereof are derived from the above mentioned alkyl groups.
  • Haloalkyl moieties are alkyl moieties which are substituted by one or more of the same or different halogen atoms and are, for example, monofluoromethyl, difluoromethyl, thfluoromethyl, monochloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2,2- difluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl, 1-fluoroethyl, 2-chloroethyl, pentafluoroethyl, l,l-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl, and typically trichloromethyl, difluorochloromethyl, difluoromethyl, thfluoromethyl and
  • Alkoxy is, for example, methoxy, ethoxy, propoxy, /so-propoxy, -butoxy, /so-butoxy, sec-butoxy and te i-butoxy, and usually methoxy or ethoxy.
  • Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2- trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy, and usually difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.
  • Alkylthio is, for example, methylthio, ethylthio, propylthio, /so-propylthio, ⁇ -butylthio,
  • Alkylsulphonyl is, for example, methylsulphonyl, ethylsulphonyl, propylsulphonyl, iso- propylsulphonyl, ⁇ -butylsulphonyl, /so-butylsulphonyl, sec-butylsulphonyl or tert- butylsulphonyl, and usually methylsulphonyl or ethylsulphonyl.
  • Alkylsulphinyl is, for example, methylsulphinyl, ethylsulphinyl, propylsulphinyl, iso- propylsulphinyl, ⁇ -butylsulphinyl, /so-butylsulphinyl, sar-butylsulphinyl or te i-butylsulphinyl, and usually methylsulphinyl or ethylsulphinyl.
  • Cycloalkyl may be saturated or partially unsaturated, preferably fully saturated, and is, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl,
  • ethoxyethyl -propoxymethyl, 7-propoxyethyl, /so-propoxymethyl or /so-propoxyethyl.
  • Aryl includes phenyl, naphthyl, anthracyl, fluorenyl and indanyl, but is usually phenyl.
  • Carbocycle includes cycloalkyl groups and aryl groups.
  • Heterocycloalkyl is a non-aromatic ring that may be saturated or partially
  • examples include oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, 1,3-dioxolanyl, 1,4-dioxanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, oxazinanyl, morpholinyl, thiomorpholinyl, imidazolidinyl, pyrazolidinyl and piperazinyl, preferably morpholinyl, pyrrolidinyl, piperdinyl and piperazinyl, more preferably morpholinyl and pyrollidinyl.
  • Heteroaryl is, for example, a monovalent monocyclic or bicyclic aromatic hydrocarbon radical.
  • monocyclic groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, and thiadiazolyl.
  • Samples of bicyclic groups include quinolinyl, cinnolinyl, quinoxalinyl, benzimidazolyl, benzothiophenyl, and benzothiadiazolyl.
  • Monocyclic heteroaryl groups are preferred, preferably pyridyl, pyrrolyl, imidazolyl and triazolyl, e.g. 1,2,4 triazolyl, pyridyl and imidazolyl being most preferred.
  • heterocycle and “heterocyclic ring” are used interchangeably and are defined to include heterocycloalkyl and heteroaryl groups. Any reference herein to a heterocycle or heterocyclic ring preferably refers to the specific examples given under the definition of heteroaryl and heterocycloalkyl above, and are preferably morpholinyl, pyrrolidinyl, piperdinyl, piperazinyl pyridyl, pyrrolyl, imidazolyl and triazolyl, e.g. 1,2,4 triazolyl, more preferably morpholinyl, pyrollidinyl, pyridyl and imidazolyl.
  • a moiety is indicated as being (optionally) substituted, e.g. alkyi, this includes those moieties where they are part of a larger group, e.g. the alkyi in the alkylthio group. The same applies, e.g. to the phenyl moiety in phenylthio etc.
  • a moiety is indicated as being optionally substituted by one or more other groups, preferably there are one to five optional substituents, more preferably one to three optional substituents.
  • a moiety is substituted by a cyclic group, e.g. aryl, heteroaryl, cycloalkyi, preferably there are no more than two such substituents, more preferably no more than one such substituent.
  • R 1 represents hydrogen, halogen, CN, SH, d-C 8 alkylthio, d-C 8 alkylsulphinyl, d-C 8 alkylsulphonyl, NH 2 , d-Cio alkyi / C 3 -C 8 cycloalkyi, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl,
  • R 8 0 carbonyl(Crd alkyi), phenyl or pyridyl, wherein the alkyi, cycloalkyi, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , NH-C r C 8 alkyi, N(C r C 8 alkyl) 2 , N0 2 , OR 8 , C r C 4 alkyi, C r C 4 haloalkyl, C 3 -C 6 cycloalkyi and a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms.
  • R 1 represents hydrogen, d-C 8 alkyi, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 3 -C 8 cycloalkyi, phenyl, pyridyl, or (R 8 0)carbonyl(d-C 4 alkyi), wherein the alkyi, alkenyl, alkynyl, cycloalkyi, phenyl and pyridyl are optionally substituted by one or more groups
  • halogen independently selected from halogen, CN, OR 8 , NH 2 , NH-C r C 8 alkyi, N(C r C 8 alkyl) 2 , C r C 4 alkyi, d-C 4 haloalkyl, C 3 -C 6 cycloalkyi and pyridyl.
  • R 1 represents hydrogen, Ci-C 4 alkyl, C 2 -C 4 alkenyl, phenyl or pyridyl, wherein the alkyl, alkenyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, OH, NH 2 , NH-Ci-C 4 alkyl, N(Ci-C 4 alkyl) 2 , C1-C4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy, Ci-C 4 haloalkoxy and C 3 -C 6 cycloalkyi.
  • R 1 represents hydrogen, CrC 4 alkyl, Ci-C 4 haloalkyl, phenyl or pyridin-2-yl, wherein the phenyl and pyridin-2-yl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy.
  • R 1 represents Ci-C 4 alkyl, C 2 -C 4 alkenyl, phenyl or pyridyl, wherein the alkyl, alkenyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, Ci-C 4 alkoxy and Ci-C 4 haloalkoxy.
  • R 1 represents hydrogen, d-C 4 alkyl, d-C 4 haloalkyl and phenyl, wherein the phenyl is optionally substituted by one or more groups
  • halogen independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy.
  • R 1 represents hydrogen, d-C 4 alkyl or phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy.
  • R 1 represents hydrogen, d-C 4 alkyl or phenyl.
  • R 2 represents hydrogen, d-C 8 alkyl, C 3 -C 8 cycloalkyi, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, benzyl, phenyl or pyridyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , N0 2 , OH, C r C alkyl, C r C haloalkyl, C r C alkoxy and C r C haloalkoxy.
  • R 2 represents hydrogen, d-C 8 alkyl, d-C 8 haloalkyl, C 3 -C 8 cycloalkyi, C 3 -C 8 halocycloalkyl, C 3 -C 8 alkenyl, C 3 -C 8 haloalkenyl, C 3 -C 8 alkynyl, C 3 -C 8 haloalkynyl, benzyl or pyridyl, wherein the benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, d-C 4 alkyl, d-C 4 haloalkyl, d-C 4 alkoxy and d-C 4 haloalkoxy.
  • R 2 represents d-C 4 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl or benzyl, wherein the alkyl, alkenyl, alkynyl and benzyl are optionally substituted by one or more groups independently selected from halogen, CN, d-C 4 alkoxy and d-C 4 haloalkoxy.
  • R 2 represents hydrogen, d-C 8 alkyl, or d-C 8 haloalkyl.
  • R 2 represents hydrogen, d-C 4 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl or benzyl, wherein the alkyl, alkenyl, alkynyl and benzyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from d-C 4 alkyl, d-C 4 haloalkyl, halogen, CN, d-C 4 alkoxy and d-C 4 haloalkoxy.
  • R 2 represents hydrogen, Ci-C 4 alkyl, C 3 -C 6 alkenyl or C3-C5 alkynyl, wherein the alkyl, alkenyl, or alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, Ci-C 4 alkoxy and Ci-C 4 haloalkoxy.
  • R 2 represents hydrogen, Ci-C 4 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl, wherein the alkyl, alkenyl, or alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy.
  • R 2 represents hydrogen, Ci-C 4 alkyl, Cs- Ce alkenyl or C 3 -C 6 alkynyl.
  • D 1 is C-Y 1 and D 2 is C-Y 2 .
  • D 1 is C-Y 1 and D 2 is N.
  • D 1 is N and D 2 is C-Y 2 .
  • D 1 is C-Y 1 and D 2 is C-Y 2 , and more preferably, D 1 and D 2 are CH.
  • R 3 represents hydrogen, halogen, CN, SH, d-C 8 alkylthio, CrC 8 alkylsulphinyl, d-C 8 alkylsulphonyl, NH 2 , C1-C10 alkyl, C 3 -C 8 cycloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl,
  • R 9 0 carbonyl(d-C 4 alkyl), phenyl or pyridyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups, e.g.
  • one to five groups independently selected from halogen, CN, NH 2 , NH-d-C 8 alkyl, N(d-C 8 alkyl) 2 , N0 2 , OR 8 , d-C 4 alkyl, d-C 4 haloalkyl, C 3 -C 6 cycloalkyl and a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms.
  • the heterocycle is preferably one as defined herein, preferably morpholinyl, pyrrolidinyl, piperdinyl, piperazinyl, pyridyl, pyrrolyl, imidazolyl or triazolyl, e.g. 1,2,4 triazolyl, more preferably morpholinyl, pyrollidinyl, pyridyl or imidazolyl.
  • R 3 represents hydrogen, d-C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 3 -C 8 cycloalkyl, phenyl, pyridyl or (R 8 0)carbonyl(d-C 4 alkyl), wherein the alkyl, alkenyl, alkynyl, cycloalkyl, phenyl and pyridyl are optionally substituted by one or more groups, e.g.
  • one to five groups independently selected from halogen, CN, OR 8 , NH 2 , NH-d-Qs alkyl, N(C r C 8 alkyl) 2 , d-C 4 alkyl, d-C 4 haloalkyl, C 3 -C 6 cycloalkyl and pyridyl.
  • R 3 represents hydrogen, d-C 4 alkyl, C 2 -C 4 alkenyl, phenyl or pyridyl, wherein the alkyl, alkenyl, phenyl and pyridyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, OH, NH 2 , NH-Cr C alkyl, N(C r C alkyl) 2 , C r C alkyl, C r C haloalkyl, C r C alkoxy, C r C haloalkoxy and C 3 -C 6 cycloalkyl.
  • groups e.g. one to five groups, independently selected from halogen, CN, OH, NH 2 , NH-Cr C alkyl, N(C r C alkyl) 2 , C r C alkyl, C r C haloalkyl, C r C alkoxy,
  • R 3 represents d-d alkyl, C 2 -C 4 alkenyl, phenyl or pyridyl, wherein the alkyl, alkenyl, phenyl and pyridyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-d alkoxy and Crd haloalkoxy.
  • R 3 represents hydrogen, d-d alkyl, d-d haloalkyl, phenyl or pyridin-2-yl, wherein the phenyl and pyridin-2-yl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy.
  • R 3 represents hydrogen, CN, d-d alkyl, C 3 -C 6 cycloalkyi, C 2 -d alkenyl, C 2 -d alkynyl, (Ci-dalkoxy)carbonyl(Ci-d alkyl), phenyl or pyridyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , NH-Ci-C 8 alkyl, N(d-C 8 alkyl) 2 , N0 2 , OH, d-d alkyl, d-d haloalkyl, C 3 -C 6 cycloalkyi, pyridyl or pyrroline
  • R 3 represents hydrogen, CN, Crd alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl or phenyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , NH-Crd alkyl, N(C r C 4 alkyl) 2 , OH, C r C 4 alkyl, C r C 4 haloalkyl, C 3 -C 6 cycloalkyi, pyridyl or pyrroline.
  • R 3 represents hydrogen, Crd alkyl, phenyl, wherein the alkyl and phenyl pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , NH-Crd alkyl, N(d-C 4 alkyl) 2 , OH, Crd alkyl, Crd haloalkyl, C 3 -C 6 cycloalkyi or pyrroline.
  • A represents group A-l, A-2, or A-3.
  • A represents group A-l, wherein A 1 represents A la or A-l represents A-2.
  • A represents group A-l.
  • a 1 represents cycle A la .
  • A represents cycle A-2 or A-3.
  • A represents cycle A-2.
  • R 4 , R 5 , R 6 and R 7 independently of one another represent hydrogen, halogen, CN, N0 2 , d-C 8 alkyl, C 3 -C 8 cycloalkyi, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, phenyl, a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms (e.g.
  • heterocycle as defined herein, preferably morpholinyl, pyrrolidinyl, piperdinyl, piperazinyl, pyridyl, pyrrolyl, imidazolyl or triazolyl, e.g.
  • 1,2,4 triazolyl more preferably morpholinyl, pyrollidinyl, pyridyl or imidazolyl), COR 9 , OR 8 , SH, Ci-C 8 -alkylthio, CrC 8 -alkylsulphinyl, CrC 8 -alkylsulphonyl, phenylthio, phenylsulphinyl, phenylsulphonyl, N(R 10 ) 2 , C0 2 R 8 , 0(CO)R 9 , CON(R 10 ) 2 , NR 10 COR 9 or CR 9 N- OR 8 , wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl and heterocycle are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, NH 2 , N0 2 , OR 8 , d-C alkyl, d-C
  • R 5 and R 6 , R 6 and R 4 , or R 7 and R 4 together with the fragment of the ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a partially or fully unsaturated 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from O, S, N and N(R 10 ), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, and wherein the ring formed by R 5 and R 6 , R 6 and R 4 , or R 7 and R 4 is optionally substituted by one or more groups, e.g.
  • one to five groups independently selected from halogen, CN, NH 2 , N0 2 , OH, C r C alkyl, d-C haloalkyl, C r C alkoxy and C r C haloalkoxy.
  • R 4 , R 5 , R 6 and R 7 independently of one another represent hydrogen, halogen, CN, OR 8 , Ci-C 8 alkyl, C 2 -C 8 alkenyl, C 3 -C 8 cycloalkyi, phenyl, pyridyl, N(R 10 ) 2 , C0 2 R 8 , NR 10 COR 9 , SH, CrC 8 -alkylthio, Ci-C 8 -alkylsulphinyl, CrC 8 -alkylsulphonyl, phenylthio, phenylsulphinyl or phenylsulphonyl, wherein the alkyl, alkenyl, cycloalkyi, phenyl and pyridyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, OR 8 , Q-C, alkyl and Q-C, haloalkyl
  • R 5 and R 6 , R 6 and R 4 , or R 4 and R 7 together with the fragment of the pyridyl ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a partially or fully unsaturated 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from O, S, N and N(R 10 ), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, wherein the ring formed by R 5 and R 6 , R 6 and R 4 , or R 4 and R 7 is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-C 4 alkyl, d-C 4 haloalkyl, d-C 4 alkoxy and Cr
  • R 4 , R 5 , R 6 and R 7 independently of one another represent hydrogen, halogen, OR 8 , CN, Q-C 4 alkyl, C 3 -C 6 cycloalkyi, N(R 10 ) 2 , phenyl, C0 2 R 8 or NR 10 COR 9 , wherein the alkyl, cycloalkyi and phenyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-C 4 alkyl, CrC 4 -haloalkyl, d-C 4 alkoxy and d-C 4 haloalkoxy;
  • A when A is A-l, wherein A 1 is A la or A l or A-2, R 5 and R 6 , R 6 and R 4 , or R 4 and R 7 , together with the fragment of the pyridyl ring to which they are attached may form a fully or partially unsaturated 5- or 6-membered carbocyclic ring optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, methyl and halomethyl.
  • R 4 , R 5 , R 6 and R 7 independently of one another represent hydrogen, halogen, OH, CN, C1-C4 alkyl, C1-C4 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 cycloalkyl, N(R 10 ) 2 , phenyl or C0 2 R 8 , wherein the alkyl, alkoxy, alkenyloxy, cycloalkyl and phenyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, C1-C4 alkyl, Ci-C 4 -haloalkyl, Ci-C 4 alkoxy and C1-C4 haloalkoxy;
  • R 4 , R 5 , R 6 and R 7 independently of one another represent hydrogen, halogen, OH, CN, Q-C, alkyl, Q-C, alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 cycloalkyl, N(R 10 ) 2 , phenyl or C0 2 R 8 , wherein the alkyl, alkoxy, alkenyloxy, cycloalkyl and phenyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-C 4 alkyl, CrC 4 -haloalkyl, d-C 4 alkoxy and CrC 4 haloalkoxy.
  • R 4 , R 5 , R 6 and R 7 independently of one another represent hydrogen, C1-C4 alkyl, CN or d-C 4 alkoxy, wherein the alkyl and alkoxy are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-C 4 alkoxy and d-C 4 haloalkoxy.
  • R 5 represents hydrogen, d-C 4 alkyl, d-C 4 haloalkyl,
  • phenyl or pyridyl wherein the phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , N0 2 , OH, Ci-C 4 alkyl, C r C 4 haloalkyl, C r C 4 alkoxy and C r C 4 haloalkoxy.
  • R 4 and R 6 independently of one another represent hydrogen, CN, OR 8 , NH 2 , halogen, C r C 8 alkyl, C r C 8 haloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 3 -C 8 cycloalkyl, SH, C r C 8 alkylthio, N(R 10 ) 2 , NR 10 COR 9 , phenyl or pyridyl, wherein phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, methyl, CN, methoxy, halomethyl and halomethoxy;
  • each R 8 independently represents one another represents hydrogen, d-C 8 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, benzyl, phenyl or pyridyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , N0 2 , OH, d-C 4 alkyl, d-C 4 - haloalkyl, d-C 4 alkoxy, d-C 4 haloalkoxy and d-C 4 -alkoxy-CrC 4 -alkyl;
  • each R 9 independently of one another represents d-C 4 -alkyl or d-C 4 haloalkyl
  • each R 10 independently of one another represent hydrogen or d-C 4 alkyl; wherein when two radicals R are attached to the same nitrogen atom, these radicals can be identical or different;
  • R 4 and R 6 independently of one another represent hydrogen, CN, OH, NH 2 , halogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy, Ci-C 4 haloalkoxy, C 3 -C 6 cycloalkyi, N(R 10 ) 2 , NR 10 COR 9 or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, methyl, CN, methoxy, halomethyl and halomethoxy;
  • each R 9 independently represents CrC 4 -alkyl or d-C 4 haloalkyl
  • each R 10 independently of one another represent hydrogen or d-C 4 alkyl
  • radicals R 10 wherein when two radicals R 10 are attached to the same nitrogen atom, these radicals can be identical or different;
  • R 4 represents hydrogen, halogen, CN, d-C 6 alkyl
  • C 3 -C 6 cycloalkyi C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, phenyl, OH, Q-C, alkoxy, NH 2 , NH(C r C alkyl), N(d-C 4 alkyl) 2 , CO(Ci-C 4 alkyl), wherein the alkyl, cycloalkyi, alkenyl, alkynyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy.
  • R 4 represents hydrogen, halogen, CN, d-C 6 alkyl, C 3 -C 6 cycloalkyi, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, phenyl, d-C 4 alkoxy or CO(d-C 4 alkyl), wherein the alkyl, cycloalkyi, alkenyl, alkynyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy.
  • R 4 represents hydrogen, halogen, CN,
  • G 1 and G 2 independently of one another represent -C(R 12 R 13 )-;
  • G 3 represents -C(R 12 R 13 )-, O, N(R 14 ) or S;
  • Each R 12 and R 13 independently of one another represent hydrogen, halogen, d-C 4 alkyl, d-C 4 haloalkyl, d-C 4 alkoxy or d-C 4 haloalkoxy.
  • R represents hydrogen, OH, d-d alkyl, d-d alkoxy, C 3 -C 6 cycloalkyl, d- alkylcarbonyl or d- haloalkylcarbonyl.
  • G 1 and G 2 independently of one another represent -C(R 12 R 13 )-;
  • G 3 represents -C(R 12 R 13 )-, O, N(R 14 ) or S;
  • each R 12 and R 13 independently of one another represent hydrogen, halogen, d-d alkyl, d-d haloalkyl, d-d alkoxy or d-d haloalkoxy;
  • R 14 represents hydrogen, OH, d-d alkyl, d-d alkoxy, C 3 -C 6 cycloalkyl, d-d alkylcarbonyl or d-d haloalkylcarbonyl.
  • G 1 , G 2 and G 3 represent C(R 3 ) 2 , wherein each R 34 independently of one another represents hydrogen or d-d alkyl.
  • G 1 represents -CH 2 -;
  • G 2 represents -C(R 12 R 13 )-
  • G 3 represents -C(R 12 R 13 )-, O, N(R 14 ) or S;
  • each R 12 and R 13 independently of one another represent hydrogen or d- a'kyl;
  • R 14 represents hydrogen or d- p represents 0, 1 or 2.
  • p is 1 or 2. More preferably, p is 1.
  • X represents X-2, X-3, X-4 or X-5.
  • X represents X-3 or X-5.
  • X represents X-3.
  • Z 4 is preferably CR 19 R 20 .
  • X is X-2 preferably one of Z 1 and Z 2 is methylene or halomethylene, preferably methylene.
  • Z 3 , Z 4 and Z 5 are independently methylene or halomethylene, preferably methylene.
  • Z 3 and Z 5 are methylene or halomethylene, preferably methylene.
  • Z 6 , Z 7 , Z 8 and Z 9 are independently methylene or halomethylene, preferably methylene.
  • Z 10 , Z 11 , Z 12 , Z 13 and Z 14 are independently methylene or halomethylene, preferably methylene.
  • Z 10 , Z 11 , Z 13 and Z 14 are independently methylene or halomethylene, preferably methylene.
  • radicals Z 1 , Z 3 , Z 6 and Z 10 are not substituted by OH; and none of Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 , Z 7 , Z 8 , Z 9 , Z 10 , Z 11 , Z 12 , Z 13 and Z 14 represent a carbon atom substituted by two OH groups.
  • Each R and R independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl, C1-C4 haloalkyl or phenyl, wherein the phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy;
  • R 15 and R 16 together with the carbon atom to which they are attached may form a
  • each R 15 and R 16 independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl or C1-C4 haloalkyl.
  • Each R 17 and R 18 independently of one another represent hydrogen, halogen, C1-C4 alkyl or C1-C4 haloalkyl.
  • each R 17 and R 18 independently of one another represent hydrogen, halogen, methyl or halomethyl.
  • Each R 19 and R 20 independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl, Q-C4 haloalkyl or phenyl, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-C 4 alkyl, C1-C4 haloalkyl, d-C 4 alkoxy and Q-C4 haloalkoxy;
  • R 19 and R 20 together with the carbon atom to which they are attached may form a C 3 -C 6 cycloalkyl group or a C 3 -C 6 halocycloalkyl group.
  • each R 19 and R 20 independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl, C1-C4 haloalkyl or phenyl, wherein the phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
  • R 19 and R 20 together with the carbon atom to which they are attached may form a C 3 -C 6 cycloalkyl group or a C 3 -C 6 halocycloalkyl group.
  • Each R 21 and R 22 independently of one another represent hydrogen, halogen, CN, OH,
  • C1-C4 alkyl, Q-C4 haloalkyl or phenyl wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-C 4 alkyl, C1-C4 haloalkyl, d-C 4 alkoxy and Q-C4 haloalkoxy.
  • each R 21 and R 22 independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl, Q-C4 haloalkyl or phenyl, wherein the phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy.
  • each R 21 and R 22 independently of one another represent halogen, C1-C4 alkyl, Q-C4 haloalkyl or phenyl, wherein the phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy.
  • Y 1 , Y 2 and ⁇ 3 independently of one another represent hydrogen, halogen, CN, N0 2 , Ci-Cs alkyl, C 3 -C 8 cycloalkyi, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, phenyl, a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms (e.g.
  • heterocycle as defined herein, preferably morpholinyl, pyrrolidinyl, piperdinyl, piperazinyl, pyridyl, pyrrolyl, imidazolyl or triazolyl, e.g.
  • 1,2,4 triazolyl more preferably morpholinyl, pyrollidinyl, pyridyl or imidazolyl), COR 9 , OR 8 , SH, Ci-Cs-alkylthio, Ci-C 8 -alkylsulphinyl, Ci-C 8 -alkylsulphonyl, phenylthio, phenylsulphinyl, phenylsulphonyl, N(R 10 ) 2 , C0 2 R 8 , 0(CO)R 9 , CON(R 10 ) 2 , NR 10 COR 9 or CR 9 N- OR 8 , wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl and heterocycle are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, NH 2 , N0 2 , OR 8 , Q-G, alkyl and Q-G,
  • Y 1 and Y 3 , or Y 2 and Y 3 together with the fragment of the pyridyl ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a partially or fully unsaturated 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from O, S, N and N(R 10 ), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms and wherein the ring formed by Y 1 and Y 3 , or Y 2 and Y 3 is optionally substituted by one or more groups, e.g.
  • one to five groups independently selected from halogen, CN, NH 2 , N0 2 , OH, Q-G, alkyl, Q-G, haloalkyl, Q-G, alkoxy and Q-G, haloalkoxy.
  • Y 1 , Y 2 and Y 3 independently of one another represent hydrogen, halogen, CN, OR 8 , G-C 8 alkyl, C 2 -C 8 alkenyl, C 3 -C 8 cycloalkyi, phenyl, pyridyl, N(R 10 ) 2 , C0 2 R 8 ,
  • NR 10 COR 9 SH, Ci-C 8 -alkylthio, C r C 8 -alkylsulphinyl, CrC 8 -alkylsulphonyl, phenylthio, phenylsulphinyl or phenylsulphonyl, wherein the alkyl, alkenyl, cycloalkyi, phenyl and pyridyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, OR 8 , CrC 4 alkyl and CrC 4 haloalkyl.
  • Y 1 , Y 2 and Y 3 independently of one another represent hydrogen, halogen, OR 8 , CN, Q-C 4 alkyl, C 3 -C 6 cycloalkyi, N(R 10 ) 2 , phenyl, C0 2 R 8 or NR 10 COR 9 , wherein the alkyl, cycloalkyi and phenyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, G-C 4 alkyl, CrC 4 -haloalkyl, G-C 4 alkoxy and CrC 4 haloalkoxy.
  • Y 1 , Y 2 , and Y 3 independently of one another represent hydrogen, halogen, OH, CN, Q-G, alkyl, Q-G, alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 cycloalkyi, N(R 10 ) 2 , phenyl or C0 2 R 8 , wherein the alkyl, alkoxy, alkenyloxy, cycloalkyi and phenyl are optionally substituted by one or more groups, e.g.
  • Y 1 , Y 2 and Y 3 independently of one another represent hydrogen, d- C 4 alkyi, CN or C1-C4 alkoxy, wherein the alkyi and alkoxy are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, Ci-C 4 alkoxy and C1-C4 haloalkoxy.
  • Y 1 and Y 2 independently of one another represent hydrogen, C1-C4 alkyi, CN or Ci-C 4 alkoxy, wherein the alkyi and alkoxy are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, Ci-C 4 alkoxy and Ci-C 4 haloalkoxy and Y 3 is as defined according to any of the defintions above.
  • Y 1 and Y 2 each represent H;
  • Y 3 represents hydrogen, halogen, CN, Ci-C 4 alkyi, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or d-C 4 alkoxy wherein the alkyi, cycloalkyl, alkenyl and alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , N0 2 , OH, C1-C4 alkyi and Q-C, haloalkyl.
  • Y 1 and Y 2 each represent H;
  • Y 3 represents hydrogen, halogen, CN, Ci-C 4 alkyi, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or d-C 4 alkoxy wherein the alkyi, cycloalkyl, alkenyl and alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , N0 2 , OH, d-C 4 alkyi and d-C 4 haloalkyl.
  • Y 1 and Y 2 each represent H;
  • Y 3 represents hydrogen, methyl, methoxy, methoxymethyl, wherein the methyl, methoxy, methoxymethyl are optionally substituted by one or more halogen.
  • Each R 8 independently of one another represents hydrogen, d-C 8 alkyi, C 3 -C 8 cycloalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl, benzyl or a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, wherein the alkyi, cycloalkyl, alkenyl, alkynyl, phenyl, benzyl and heterocycle are optionally substituted by one or more groups, e.g.
  • the heterocycle is preferably one as defined herein, preferably morpholinyl, pyrrolidinyl, piperdinyl, piperazinyl, pyridyl, pyrrolyl, imidazolyl or triazolyl, e.g. 1,2,4 triazolyl, more preferably morpholinyl, pyrollidinyl, pyridyl or imidazolyl.
  • each R 8 independently of one another represents hydrogen, d-C 8 alkyi, d-C 8 haloalkyl, C 3 -C 8 alkenyl, C 3 -C 8 haloalkenyl, C 3 -C 8 haloalkynyl, phenyl, benzyl or pyridyl, wherein the phenyl, benzyl and pyridyl are optionally substituted by one or more groups, e.g.
  • one to five groups independently selected from halogen, CN, NH 2 , N0 2 , OH, d-d alkyl, d-d-haloalkyl, d-d alkoxy and d-d haloalkoxy.
  • each R 8 independently of one another represents hydrogen, Ci-Cs alkyl, Ci-Cs haloalkyl, C 3 -C 8 alkenyl, C 3 -C 8 haloalkenyl, C 3 -C 8 alkynyl, C 3 -C 8 haloalkynyl, phenyl, benzyl, or pyridyl, wherein the phenyl, benzyl and pyridyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-d alkyl, d-d-haloalkyl, d-d alkoxy and d-d haloalkoxy.
  • each R 8 independently of one another represents hydrogen, d-d alkyl or d-d haloalkyl.
  • each R 8 independently of one another represents hydrogen, Ci-C 8 alkyl, C 3 -C 8 cycloalkyi, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl, benzyl or pyridyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , N0 2 , OH, d-d alkyl, d-d-haloalkyl, d-d alkoxy, d-d haloalkoxy and Crd-alkoxy-Crd-alkyl.
  • each R 8 independently of one another represents hydrogen, Crd alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, phenyl or benzyl.
  • Each R 9 independently of one another represents hydrogen, d-C 8 alkyl, C 3 -C 8 cycloalkyi, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, phenyl, benzyl or pyridyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl, benzyl and pyridyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, NH 2 , N0 2 , OH, d-d alkyl, Crd haloalkyl, Cr alkoxy and Crd haloalkoxy.
  • each R 9 independently of one another represents hydrogen, d-C 8 alkyl or Ci-C 8 haloalkyl.
  • each R 9 independently of one another represents hydrogen, Cr alkyl or Crd haloalkyl.
  • Each R 10 independently of one another represents hydrogen, OH, d-C 8 alkyl, d-C 8 alkoxy, CrC 8 -alkoxy-Crd-alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, or COR 9 , wherein the alkyl, alkoxy, alkenyl and alkynyl are optionally substituted by one or more halogen; wherein when two radicals R 10 are attached to the same nitrogen atom, these radicals can be identical or different; wherein when two radicals R 10 are attached to the same nitrogen atom, both of these radicals cannot be OH, Cr alkoxy or Crd haloalkoxy; and wherein when two radicals R 10 are attached to the same nitrogen atom, these two radicals together with the nitrogen atom to which they are attached may form a cycle B-l, B-2, B-3, B-4, B-5, B-6, B-7 or B-8:
  • groups e.g. one to five groups, independently selected from halogen, CN, NH 2 , N0 2 , OH, d-d alkyl, d-d haloalkyi, d-d alkoxy and d-d haloalkoxy.
  • each R 10 independently of one another represents hydrogen, d-C 8 alkyl or
  • each R 10 independently of one another represents hydrogen or d-d alkyl; wherein when two radicals R 10 are attached to the same nitrogen atom, these radicals can be identical or different; and wherein when two radicals R 10 are attached to the same nitrogen atom, these two radicals together with the nitrogen atom to which they are attached may form a cycle B-1, B-2, B-3, B-4 or B-5 wherein the cycle formed is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, methyl and halomethyl.
  • R 1 represents hydrogen, d-C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 3 -C 8 cycloalkyi, phenyl, pyridyl or (R 8 0)carbonyl(d-C 4 alkyl), wherein the alkyl, alkenyl, alkynyl, cycloalkyi, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, OR 8 , NH 2 , NH-C r C 8 alkyl, N(C r C 8 alkyl) 2 , C r C 4 alkyl, C r C 4 haloalkyi, C 3 -C 6 cycloalkyi and pyridyl;
  • R 2 represents hydrogen, d-C 8 alkyl, d-C 8 haloalkyi, C 3 -C 8 cycloalkyi, C 3 -C 8 halocycloalkyl, C 3 -C 8 alkenyl, C 3 -C 8 haloalkenyl, C 3 -C 8 alkynyl, C 3 -C 8 haloalkynyl, benzyl or pyridyl, wherein the benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, Crd alkyl, d-C 4 haloalkyi, Crd alkoxy and d-C 4 haloalkoxy;
  • R 3 represents hydrogen, d-C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 3 -C 8 cycloalkyi, phenyl, pyridyl, or (R 8 0)carbonyl(d-C 4 alkyl), wherein the alkyl, alkenyl, alkynyl, cycloalkyi, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, OR 8 , NH 2 , NH-Ci-C 8 alkyl, N(d-C 8 alkyl) 2 , d-C alkyl, d-C haloalkyl, C 3 -C 6 cycloalkyl and pyridyl;
  • A represents group A-l, A-2, or A-3;
  • R 4 , R 5 , R 6 and R 7 independently of one another represent hydrogen, halogen, CN,
  • OR 8 Ci-Cs alkyl, C 2 -C 8 alkenyl, C 3 -C 8 cycloalkyl, phenyl, pyridyl, N(R 10 ) 2 , C0 2 R 8 , NR 10 COR 9 , SH, Ci-Cs-alkylthio, Ci-C 8 -alkylsulphinyl, Ci-C 8 -alkylsulphonyl, phenylthio, phenylsulphinyl or phenylsulphonyl, wherein the alkyl, alkenyl, cycloalkyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, OR 8 , Ci-C 4 alkyl and d-C 4 haloalkyl;
  • R 5 and R 6 , R 6 and R 4 , or R 4 and R 7 together with the fragment of the pyridyl ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a partially or fully unsaturated 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from O, S, N and N(R 10 ), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, wherein the ring formed by R 5 and R 6 , R 6 and R 4 , or R 4 and R 7 is optionally substituted by one or more groups independently selected from halogen, CN, d-C 4 alkyl, Q- C 4 haloalkyl, d-C 4 alkoxy and CrC 4 haloal
  • X represents X-3 or X-5;
  • each R 15 and R 16 independently of one another represent hydrogen, halogen, CN, OH, Ci-C, alkyl or Q-C, haloalkyl;
  • each R 17 and R 18 independently of one another represent hydrogen, halogen, d-C 4 alkyl or d-C 4 haloalkyl;
  • each R 19 and R 20 independently of one another represent hydrogen, halogen, CN, OH, d-C 4 alkyl, d-C 4 haloalkyl or phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
  • R 19 and R 20 together with the carbon atom to which they are attached may form a C 3 -C 6 cycloalkyl group or a C 3 -C 6 halocycloalkyl group;
  • Y 1 , Y 2 and Y 3 independently of one another represent hydrogen, halogen, CN, OR 8 , Ci-C 8 alkyl, C 2 -C 8 alkenyl, C 3 -C 8 cycloalkyl, phenyl, pyridyl, N(R 10 ) 2 , C0 2 R 8 , NR 10 COR 9 , SH, Q- C 8 -alkylthio, CrC 8 -alkylsulphinyl, d-C 8 -a I kyl sulphonyl, phenylthio, phenylsulphinyl or phenylsulphonyl, wherein the alkyl, alkenyl, cycloalkyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, OR 8 , d-d alkyl and Crd haloalkyl;
  • each R 8 independently of one another represents hydrogen, d-C 8 alkyl, d-C 8 haloalkyl, C 3 -C 8 alkenyl, C 3 -C 8 haloalkenyl, C 3 -C 8 haloalkynyl, phenyl, benzyl or pyridyl, wherein the phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , N0 2 , OH, d-d alkyl, d-d-haloalkyl, d-d alkoxy and d-d haloalkoxy;
  • each R 9 independently of one another represents hydrogen, Ci-C 8 alkyl or Ci-C 8 haloalkyl
  • each R 10 independently of one another represents hydrogen, Ci-C 8 alkyl or COR 9 ; wherein when two radicals R 10 are attached to the same nitrogen atom, these radicals can be identical or different;
  • R 1 represents hydrogen, Crd alkyl, C 2 -C 4 alkenyl, phenyl or pyridyl, wherein the alkyl, alkenyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, OH, NH 2 , NH-C r C 4 alkyl, N(C r C 4 alkyl) 2 , C r C 4 alkyl, Crd haloalkyl, Crd alkoxy, Crd haloalkoxy and C 3 -C 6 cycloalkyl;
  • R 2 represents d-C 4 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl or benzyl, wherein the alkyl, alkenyl, alkynyl and benzyl are optionally substituted by one or more groups independently selected from halogen, CN, Crd alkoxy and Crd haloalkoxy;
  • R 3 represents hydrogen, Crd alkyl, C 2 -C 4 alkenyl, phenyl or pyridyl, wherein the alkyl, alkenyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, OH, NH 2 , NH-C r C 4 alkyl, N(C r C 4 alkyl) 2 , C r C 4 alkyl, d-C 4 haloalkyl, Crd alkoxy, Crd haloalkoxy and C 3 -C 6 cycloalkyl;
  • A represents group A-l, A-2, or A-3;
  • R 4 , R 5 , R 6 and R 7 independently of one another represent hydrogen, halogen, OR 8 , CN, d-d alkyl, C 3 -C 6 cycloalkyl, N(R 10 ) 2 , phenyl, C0 2 R 8 or NR 10 COR 9 , wherein the alkyl, cycloalkyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, Crd alkyl, d-C 4 -haloalkyl, Crd alkoxy and d-C 4 haloalkoxy; or, when A is A-l, wherein A 1 is A la or A l , or when A is A-2, R 5 and R 6 , R 6 and R 4 , or
  • R 4 and R 7 together with the fragment of the pyridyl ring to which they are attached may form a fully or partially unsaturated 5- or 6-membered carbocyclic ring, optionally substituted by one or more groups independently selected from halogen, methyl and halomethyl;
  • X represents X-3
  • each R 15 and R 16 independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl or C1-C4 haloalkyi;
  • each R 17 and R 18 independently of one another represent hydrogen, halogen, C1-C4 alkyl or C1-C4 haloalkyi;
  • each R 19 and R 20 independently of one another represent hydrogen, halogen, CN, OH,
  • R 19 and R 20 together with the carbon atom to which they are attached may form a C 3 -C 6 cycloalkyl group or a C 3 -C 6 halocycloalkyl group;
  • Y 1 , Y 2 and Y 3 independently of one another represent hydrogen, halogen, OR 8 , CN, C1-C4 alkyl, C 3 -C 6 cycloalkyl, N(R 10 ) 2 , phenyl, C0 2 R 8 or NR 10 COR 9 wherein the alkyl, cycloalkyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, d-C 4 alkyl, CrC 4 -haloalkyl, d-C 4 alkoxy and CrC 4 haloalkoxy;
  • each R 8 independently of one another represents hydrogen, d-C 8 alkyl, d-C 8 haloalkyi, C 3 -C 8 alkenyl, C 3 -C 8 haloalkenyl, C 3 -C 8 alkynyl, C 3 -C 8 haloalkynyl, phenyl, benzyl, or pyridyl, wherein the phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, d-C 4 alkyl, d-C 4 -haloalkyl, d-C 4 alkoxy and d-C 4 haloalkoxy;
  • each R 9 independently of one another represents hydrogen, d-C 4 alkyl or d-C 4 haloalkyi;
  • each R 10 independently of one another represents hydrogen or d-C 4 alkyl
  • radicals R 10 wherein when two radicals R 10 are attached to the same nitrogen atom, these radicals can be identical or different;
  • R 1 represents hydrogen, C1-C4 alkyl, C1-C4 haloalkyi, phenyl or pyridin-2-yl, wherein the phenyl and pyridin-2-yl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
  • R 2 represents hydrogen, Ci-C 8 alkyl, or Ci-C 8 haloalkyi
  • R 3 represents hydrogen, d-d alkyl, d-d haloalkyi, phenyl or pyridin-2-yl, wherein the phenyl and pyridin-2-yl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
  • A represents group A-l, A-2 or A-3;
  • R 4 , R 5 , R 6 and R 7 independently of one another represent hydrogen, halogen, OH, CN, Ci-d alkyl, Crd alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 cycloalkyi, N(R 10 ) 2 , phenyl or C0 2 R 8 , wherein the alkyl, alkoxy, alkenyloxy, cycloalkyi and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, Crd alkyl, d-C 4 -haloalkyl, Ci- alkoxy and d-d haloalkoxy;
  • X represents X-3
  • each R 15 and R 16 independently of one another represent hydrogen, halogen, CN, OH, d-d alkyl or C r C 4 haloalkyi;
  • each R 17 and R 18 independently of one another represent hydrogen, halogen, methyl or halomethyl
  • each R 19 and R 20 independently of one another represent hydrogen, halogen, CN, OH, d-d alkyl, d-C 4 haloalkyi or phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
  • R 19 and R 20 together with the carbon atom to which they are attached may form a
  • Y 1 , Y 2 , and Y 3 independently of one another represent hydrogen, halogen, OH, CN, d-d alkyl, C r C 4 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 cycloalkyi, N(R 10 ) 2 , phenyl or C0 2 R 8 , wherein the alkyl, alkoxy, alkenyloxy, cycloalkyi and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, Crd alkyl, d-C 4 -haloalkyl, Crd alkoxy and d-C 4 haloalkoxy;
  • each R 8 independently or one another represents hydrogen, Crd alkyl or Crd haloalkyi
  • each R 10 independently of one another represents hydrogen or Crd alkyl; wherein when two radicals R are attached to the same nitrogen atom, these radicals can be identical or different;
  • R 1 represents Ci-C 4 alkyl, C 2 -C 4 alkenyl, phenyl or pyridyl, wherein the alkyl, alkenyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, Ci-C 4 alkoxy and Ci-C 4 haloalkoxy.
  • R 3 represents pyridyl, optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , N0 2 , OH, Ci-C 4 alkyl, Ci-C 4 haloalkyl, d-C 4 alkoxy, CrC 4 haloalkoxy, C 3 -C 6 cycloalkyl and a 5- or 6-membered
  • heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms.
  • the heterocycle is preferably one as defined herein, preferably morpholinyl, pyrrolidinyl, piperdinyl, piperazinyl, pyridyl, pyrrolyl, imidazolyl or triazolyl, e.g. 1,2,4 triazolyl, more preferably morpholinyl, pyrollidinyl, pyridyl or imidazolyl.
  • R 3 represents pyridin-2-yl, optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , N0 2 , OH, CrC 4 -alkyl, CrC 4 -haloalkyl, d-C 4 -alkoxy, CrC 4 -haloalkoxy, C 3 -C 6 cycloalkyl and a 5 or 6- membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms.
  • the heterocycle is preferably one as defined herein, preferably morpholinyl, pyrrolidinyl, piperdinyl, piperazinyl, pyridyl, pyrrolyl, imidazolyl or triazolyl, e.g. 1,2,4 triazolyl, more preferably morpholinyl, pyrollidinyl, pyridyl or imidazolyl.
  • X represents X-3
  • Z 3 and Z 5 represent methylene
  • each R 17 and R 18 independently of one another represent hydrogen, halogen, methyl or halomethyl;
  • each R 19 and R 20 independently of one another represent hydrogen, halogen, CN, OH,
  • R 19 and R 20 together with the carbon atom to which they are attached may form a C3-C5 cycloalkyl group optionally substituted by halogen.
  • Y 1 and Y 3 , Y 2 and Y 3 , R 5 and R 6 , R 6 and R 4 , or R 4 and R 7 together with the fragment of the pyridyl ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from O, S, N and N(R 5 ), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, and wherein the ring formed by Y 1 and Y 3 , Y 2 and Y 3 , R 5 and R 6 , R 6 and R 4 , or R 4 and R 7 is optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , N0 2 , OH, d-C 4 alkyl, d-C 4 halo
  • Y 1 and Y 3 , Y 2 and Y 3 , R 5 and R 6 , R 6 and R 4 , or R 4 and R 7 together with the fragment of the ring to which they are attached may form a fully or partially unsaturated 6-membered carbocyclic ring optionally substituted by one or more groups independently selected from halogen, methyl and halomethyl.
  • R 5 and R 6 , R 6 and R 4 , or R 4 and R 7 together with the fragment of the ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from O, S, N and N(R 5 ), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, and wherein the ring formed by R 5 and R 6 , R 6 and R 4 , or R 4 and R 7 is optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , N0 2 , OH, Q-G, alkyl, C r C haloalkyl, Q-G, alkoxy and Q-G, haloalkoxy.
  • R 5 and R 6 , R 6 and R 4 , or R 4 and R 7 together with the fragment of the ring to which they are attached may preferably form a fully or partially unsaturated 6-membered carbocyclic ring optionally substituted by one or more groups independently selected from halogen, methyl and halomethyl.
  • any group of compounds wherein R 5 and R 6 , R 6 and R 4 , or R 4 and R 7 , together with the fragment of the ring to which they are attached may form ring, preferably this ring will only be formed by R 5 and R 6 together with the fragment of the ring to which they are attached.
  • R 1 represents hydrogen, C 1 -C4 alkyl, C 1 -C4 haloalkyl and phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
  • R 2 represents hydrogen, d-d alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl, wherein the alkyl, alkenyl, or alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, d-d alkoxy and d-d haloalkoxy;
  • D 1 represents C-Y 1 ;
  • D 2 represents C-Y 2 ;
  • A represents group A-l, A-2, or A-3;
  • a 1 represents the cycle A la , A l , or A lc ;
  • R 3 represents hydrogen, CN, d-d alkyl, C 3 -C 6 cycloalkyi, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, (CrC 4 alkoxy)carbonyl(d-C 4 alkyl), phenyl or pyridyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , NH-C r C 8 alkyl, N(C r C 8 alkyl) 2 , N0 2 , OH, C r C 4 alkyl, C r C 4 haloalkyl, C 3 -C 6 cycloalkyi, pyridyl or pyrroline;
  • R 4 represents hydrogen, halogen, CN, Ci-C 6 alkyl, C 3 -C 6 cycloalkyi, C 2 -C 6 alkenyl, C 2 - C 6 alkynyl, phenyl, OH, C r C 4 alkoxy, NH 2 , NH(C r C 4 alkyl), N(C r C 4 alkyl) 2 , CO(C r C 4 alkyl), wherein the alkyl, cycloalkyi, alkenyl, alkynyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
  • R 5 represents hydrogen, halogen, CN, Ci-C 8 alkyl, C 3 -C 6 cycloalkyi, C 2 -C 8 alkenyl, C 2 - C 8 alkynyl, phenyl, pyridyl, CO(C r C 4 alkyl), OH, C r C 4 alkoxy, NH 2 , NH(C r C 4 alkyl), N(C r C 4 alkyl) 2 or C0 2 (d-C 4 alkyl), wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , OR 8 , Ci-d alkyl, C r C 4 haloalkyl;
  • R 6 represents hydrogen, halogen, CN, Ci-d alkyl, C 3 -C 6 cycloalkyi, C 2 -C 6 alkenyl, C 2 - C 6 alkynyl, phenyl, Crd alkoxy or benzyloxy, wherein the alkyl, cycloalkyi, alkenyl, alkynyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
  • R 5 and R 6 together with the fragment of the ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a partially or fully unsaturated 5- to 7-membered heterocyclic ring containing one heteroatom independently selected from O, S, N NH and N(d-C 4 alkyl), wherein the ring formed is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
  • R 7 represents hydrogen, halogen, CN, Q-C4 alkyi, C 3 -C 6 cycloalkyi, C 2 -C 4 alkenyl, C 2 - C 4 alkynyl, OH, C r C 4 alkoxy, NH 2 , NH(C r C 4 alkyi), N(C r C 4 alkyl) 2 , C0 2 (C r C 4 alkyi) and C0 2 (Ci-
  • G 1 and G 2 independently of one another represent -C(R 12 R 13 )-;
  • G 3 represents -C(R 12 R 13 )-, O, N(R 14 ) or S;
  • each R 12 and R 13 independently of one another represent hydrogen, halogen, Ci-C 4 alkyi, Ci-C 4 haloalkyl, Ci-C 4 alkoxy or Ci-C 4 haloalkoxy;
  • R 14 represents hydrogen, OH, Ci-C 4 alkyi, Ci-C 4 alkoxy, C 3 -C 6 cycloalkyi, Ci-C 8 alkylcarbonyl or Ci-C 8 haloalkylcarbonyl;
  • p 1 or 2;
  • X represents X-3
  • Z 4 represent CR 19 R 20 ;
  • each R 15 and R 16 independently of one another represent hydrogen, halogen, d-C 4 alkyi or d-C 4 haloalkyl;
  • each R 17 and R 18 independently of one another represent hydrogen, halogen, methyl or halomethyl
  • each R 19 , R 20 independently of one another represent hydrogen, halogen, CN, OH,
  • R 19 and R 20 together with the carbon atom to which they are attached may form a C 3 -C 6 cycloalkyi group or a C 3 -C 6 halocycloalkyl group;
  • Y 1 and Y 2 each represent H
  • Y 3 represents hydrogen, halogen, CN, Ci-C 4 alkyi, C 3 -C 6 cycloalkyi, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or d-C 4 alkoxy wherein the alkyi, cycloalkyi, alkenyl and alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , N0 2 , OH, Ci-C, alkyi and Q-C, haloalkyl;
  • each R 8 independently of one another represents hydrogen, d-C 8 alkyi, C 3 -C 8 cycloalkyi, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl, benzyl or pyridyl, wherein the alkyi, cycloalkyi, alkenyl, alkynyl, phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , N0 2 , OH, d-C 4 alkyi, d-C 4 - haloalkyl, d-C 4 alkoxy, CrC 4 haloalkoxy and CrC 4 -alkoxy-CrC 4 -alkyl.
  • R 1 represents hydrogen, C 1 -C4 alkyl, C 1 -C4 haloalkyl and phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
  • R 2 represents hydrogen, d-d alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl, wherein the alkyl, alkenyl, or alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
  • D 1 represents C-Y 1 ;
  • D 2 represents C-Y 2 ;
  • A represents group A-l, A-2, or A-3;
  • a 1 represents the cycle A la , A l , or A lc ;
  • R 3 represents hydrogen, CN, d-d alkyl, C 2 -d alkenyl, C 2 -d alkynyl or phenyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl and phenyl pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , NH-Crd alkyl, N(Crd alkyl) 2 , OH, Crd alkyl, Crd haloalkyl, C 3 -C 6 cycloalkyi, pyridyl or pyrroline;
  • R 4 represents hydrogen, halogen, CN, Ci-C 6 alkyl, C 3 -C 6 cycloalkyi, C 2 -C 4 alkenyl, C 2 -
  • R 5 represents hydrogen, halogen, CN, Ci-C 8 alkyl, C 3 -C 6 cycloalkyi, C 2 -C 8 alkenyl, C 2 - C 8 alkynyl, phenyl, pyridyl, CO(C r C 4 alkyl), OH, Crd alkoxy, NH 2 , NH(C r C 4 alkyl), N(C r C 4 alkyl) 2 or C0 2 (d-C 4 alkyl), wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , OR 8 , d-d alkyl, C r C 4 haloalkyl;
  • R 6 represents hydrogen, halogen, CN, d-C 4 alkyl, Crd alkoxy or benzyloxy, wherein the alkyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
  • R 5 and R 6 together with the fragment of the ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a partially or fully unsaturated 5- to 7-membered heterocyclic ring containing one heteroatom independently selected from O or S, wherein the ring formed is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
  • R 7 represents hydrogen, halogen, CN, d-C4 alkyl, C 3 -C 6 cycloalkyi, C 2 -C 4 alkenyl, C 2 - d alkynyl, OH, C r C 4 alkoxy, NH 2 , NH(C r C 4 alkyl), N(C r C 4 alkyl) 2 , C0 2 (C r C 4 alkyl) and C0 2 (d-C 4 alkyl), wherein the alkyl, cycloalkyi, alkenyl and alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
  • G 1 represents -CH 2 -;
  • G 2 represents -C(R 12 R 13 )-
  • G 3 represents -C(R 12 R 13 )-, O, N(R 14 ) or S;
  • each R 12 and R 13 independently of one another represent hydrogen or C1-C4 alkyl
  • R 14 represents hydrogen or d-d alkyl
  • p 1 or 2;
  • X represents X-3
  • Z 4 represent CR 19 R 20 ;
  • each R 15 and R 16 independently of one another represent hydrogen, halogen, Crd alkyl or Crd haloalkyl;
  • each R 17 and R 18 independently of one another represent hydrogen, halogen, methyl or halomethyl
  • each R 19 , R 20 independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl or CHd haloalkyl;
  • R 19 and R 20 together with the carbon atom to which they are attached may form a C 3 -C 6 cycloalkyi group or a C 3 -C 6 halocycloalkyl group;
  • grouping X-3 contains at most one ring which contains either only one of the radicals Z 3 to Z 5 or two radicals Z 3 to Z 5 or three radicals Z 3 to Z 5 as ring members;
  • Y 1 and Y 2 each represent H
  • Y 3 represents hydrogen, halogen, CN, Crd alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or Crd alkoxy wherein the alkyl, cycloalkyi, alkenyl and alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , N0 2 , OH, Crd alkyl and Crd haloalkyl;
  • each R 8 independently of one another represents hydrogen, d-C 6 alkyl, C 3 -C 6 alkenyl, C 3 -d alkynyl, phenyl or benzyl.
  • the invention also rovides compounds of formula I-i
  • the invention also rovides compounds of formula I-ii
  • R 4 , R 5 and R 6 , and preferred defintiions thereof, are as defined for pounds of formula I.
  • the invention also rovides compounds of formula I-iii
  • D 1 , D 2 , X, Y 1 , Y 2 , Y 3 , R 1 and R 2 are as defined herein for compounds of formula (I); or a salt or N-oxide thereof.
  • the preferred definitions of X, Y 1 , Y 2 , Y 3 , R 1 and R 2 defined in respect of compounds of formula (I) also apply to compounds of formula (II).
  • the invention provides a compound of formula (III) wherein T 1 and T 2 independently of one another represent Ci-C 8 alkoxy, or T 1 and T 2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-Ci-C 6 -alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C 6 alkyl;
  • D 1 , D 2 , A, X, Y 1 , Y 2 , Y 3 and R 1 are as defined herein for compounds of formula (I); or a salt or N-oxide thereof.
  • the preferred definitions of A, R 1 , X, Y 1 , Y 2 , Y 3 and R 2 defined in respect of compounds of formula (I) also apply to compounds of formula (III).
  • the invention provides a compound of formula (IV)
  • X' represents X'-l, X'-2 or X'-3
  • D 1 , D 2 , A, Z 3 , Z 6 , Z 7 , Z 10 , Z 11 , Z 12 , Y 1 , Y 2 , Y 3 , R 1 and R 2 are as defined herein for compounds of formula (I); or a salt or N-oxide thereof.
  • the preferred definitions of A, Z 3 , Z 6 , Z 7 , Z 10 , Z 11 , Z 12 , Y 1 , Y 2 , Y 3 , R 1 and R 2 defined in respect of compounds of formula (I) also apply to compounds of formula (VI).
  • the invention provides a compound of formula (V)
  • X' represents X'-l, X'-2 or X'-3 #— ⁇ —# #— ⁇ — ⁇ —# #— ⁇ — ⁇ — ⁇ —#
  • ⁇ 1 and ⁇ 2 independently of one another represent CrC 8 alkoxy, or T 1 and T 2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC 6 -alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C 6 alkyl;
  • D 1 , D 2 , A, Z 3 , Z 6 , Z 7 , Z 10 , Z 11 , Z 12 , Y 1 , Y 2 , Y 3 and R 1 are as defined herein for a compound of formula (I); or a salt or N-oxide thereof.
  • the preferred definitions of A, Z 3 , Z 6 , Z 7 , Z 10 , Z 11 , Z 12 , Y 1 , Y 2 , Y 3 and R 1 defined in respect of compounds of formula (I) also apply to compounds of formula (V).
  • the invention provides a compound of formula (VI)
  • X' represents X'-l, X'-2 or X'-3
  • R 23 and R 24 independently of one another represent hydrogen, halogen, CN, Q-C 4 alkyl, Ci-C 4 haloalkyl or phenyl, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-C 4 alkyl, CrC 4 haloalkyl, Q-C 4 alkoxy and CrC 4 haloalkoxy;
  • D 1 , D 2 , A, Z 3 , Z 6 , Z 7 , Z 10 , Z 11 , Z 12 , Y 1 , Y 2 , Y 3 , R 1 and R 2 are as defined herein for a compound of formula (I); or a salt or N-oxide thereof.
  • the preferred definitions of A, Z 3 , Z 6 , Z 7 , Z 10 , Z 11 , Z 12 , Y 1 , Y 2 , Y 3 , R 1 and R 2 defined in respect of compounds of formula (I) also apply to compounds of formula (VI).
  • the invention provides a compound of formula (VII)
  • X' represents X'-l, X'-2 or X'-3
  • R 23 and R 24 independently of one another represent hydrogen, halogen, CN, Ci-C 4 alkyl, Q- haloalkyl or phenyl, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-C 4 alkyl, CrC 4 haloalkyl, d-C 4 alkoxy and CrC 4 haloalkoxy;
  • T 1 and T 2 independently of one another represent CrC 8 alkoxy, or T 1 and T 2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC 6 -alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C 6 alkyl;
  • D 1 , D 2 , A, Z 3 , Z 6 , Z 7 , Z 10 , Z 11 , Z 12 , Y 1 , Y 2 , Y 3 and R 1 are as defined herein for compounds of formula (I); or a salt or N-oxide thereof.
  • the preferred definitions of A, Z 3 , Z 6 , Z 7 , Z 10 , Z 11 , Z 12 , Y 1 , Y 2 , Y 3 and R 1 defined in respect of compounds of formula (I) also apply to compounds of formula (VII).
  • the invention provides a compound of formula (VIII)
  • X' represents X'-l, X'-2 or X'-3
  • D 1 , D 2 , Z 3 , Z 6 , Z 7 , Z 10 , Z 11 , Z 12 , Y 1 , Y 2 , Y 3 , R 1 and R 2 are as defined herein for a compound of formula (I); or a salt or N-oxide thereof.
  • the preferred definitions of Z 3 , Z 6 , Z 7 , Z 10 , Z 11 , Z 12 , Y 1 , Y 2 , Y 3 , R 1 and R 2 defined in respect of compounds of formula (I) also apply to compounds of formula (VIII).
  • the invention provides a compound of formula (IX)
  • X' represents X'-l, X'-2 or X'-3
  • D 1 , D 2 , Z 3 , Z 6 , Z 7 , Z 10 , Z 11 , Z 12 , Y 1 , Y 2 , Y 3 , R 1 and R 2 are as defined herein for a compound of formula (I); or a salt or N-oxide thereof.
  • the preferred definitions of Z 3 , Z 6 , Z 7 , Z 10 , Z 11 , Z 12 , Y 1 , Y 2 , Y 3 , R 1 and R 2 defined in respect of compounds of formula (I) also apply to compounds of formula (IX).
  • the invention provides a compound of formula (X)
  • X' represents X'-l, X'-2 or X'-3
  • D 1 , D 2 , Z 3 , Z 6 , Z 7 , Z 10 , Z 11 , Z 12 , Y 1 , Y 2 , Y 3 , R 1 and R 2 are as defined herein for a compound of formula (I); or a salt or N-oxide thereof.
  • the preferred definitions of Z 3 , Z 6 , Z 7 , Z 10 , Z 11 , Z 12 , Y 1 , Y 2 , Y 3 , R 1 and R 2 defined in respect of compounds of formula (I) also apply to compounds of formula (X).
  • the invention provides a compound of formula (XI)
  • R is a halogen or a sulfonic acid ester group, e.g. bromine, iodine, mesylate, triflate, phenylsulfonic acid ester or nonafluorobutylsulfonic acid ester, wherein the phenylsulfonic acid ester is optionally substituted by one or more groups independently selected from halogen, N0 2 , CN, d-d alkyl, d-d haloalkyl, Ci-d alkoxy and d-d haloalkoxy, for example tosylate or nitro-phenylsulfonic acid ester;
  • a halogen or a sulfonic acid ester group e.g. bromine, iodine, mesylate, triflate, phenylsulfonic acid ester or nonafluorobutylsulfonic acid ester, wherein the phenylsulfonic acid ester is optional
  • T 1 and T 2 independently of one another represent d-C 8 alkoxy, or T 1 and T 2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-Ci-C 6 -alkylidene-0) whereby the alkylidene fragment, wherein the alkylidene fragment is optionally substituted by one to four d-C 6 alkyl;
  • X' represents X'-l, X'-2 or X'-3
  • D 1 , D 2 , Z 3 , Z 6 , Z 7 , Z 10 , Z 11 , Z 12 , Y 1 , Y 2 , Y 3 and R 1 are as defined herein for a compound of formula (I); or a salt or N-oxide thereof.
  • the preferred definitions of Z 3 , Z 6 , Z 7 , Z 10 , Z 11 , Z 12 , Y 1 , Y 2 , Y 3 and R 2 defined in respect of compounds of formula (I) also apply to compounds of formula (XI).
  • the invention provides a compound of formula (XII) wherein X' represents X'-l, X'-2 or X'-3
  • A, Z 3 , Z 6 , Z 7 , Z 10 , Z 11 and Z 12 are as defined herein for a compound of formula (I); or a salt or N-oxide thereof.
  • the preferred definitions of A, Z 3 , Z 6 , Z 7 , Z 10 , Z 11 and Z 12 defined in respect of compounds of formula (I) also apply to compounds of formula (XII).
  • the invention provides a compound of formula (XIII)
  • X' represents X'-l, X'-2 or X'-3 #— ⁇ —# #— ⁇ — ⁇ —# #— ⁇ — ⁇ — ⁇ —#
  • ⁇ 1 and ⁇ 2 independently of one another represent CrC 8 alkoxy, or T 1 and T 2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC 6 -alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C 6 alkyl;
  • D 1 , D 2 , Z 3 , Z 6 , Z 7 , Z 10 , Z 11 , Z 12 , Y 1 , Y 2 , Y 3 and R 1 are as defined herein for a compound of formula (I); or a salt or N-oxide thereof.
  • the preferred definitions of Z 3 , Z 6 , Z 7 , Z 10 , Z 11 , Z 12 , Y 1 , Y 2 , Y 3 and R 1 defined in respect of compounds of formula (I) also apply to compounds of formula (XII).
  • the invention provides a compound of formula (XV)
  • R is a halogen or a sulfonic acid ester group, e.g. bromine, iodine, mesylate, tosylate, triflate, phenylsulfonic acid ester, nitro-phenylsulfonic acid ester, or nonafluorobutylsulfonic acid ester, wherein the phenylsulfonic acid ester is optionally substituted by one or more groups independently selected from halogen, N0 2 , CN, d-d alkyl, d-d haloalkyl, d-d alkoxy and d-d haloalkoxy, for example tosylate or nitro- phenylsulfonic acid ester;
  • a halogen or a sulfonic acid ester group e.g. bromine, iodine, mesylate, tosylate, triflate, phenylsulfonic acid ester, nitro-pheny
  • X' represents X'-l, X'-2 or X'-3
  • R 23 and R 24 independently of one another represent hydrogen, halogen, CN, Ci-d alkyl, Ci-d haloalkyl or phenyl, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, Crd alkyl, d-d haloalkyl, Crd alkoxy and Crd haloalkoxy;
  • T 1 and T 2 independently of one another represent d-C 8 alkoxy, or T 1 and T 2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-Ci-C 6 -alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C 6 alkyl; D 1 , D 2 , Z 3 , Z 6 , Z 7 , Z 10 , Z 11 , Z 12 , Y 1 , Y 2 , Y 3 and R 1 are as defined herein for a compound of formula (I); or a salt or N-oxide thereof.
  • the compound of formula (XV) is a compound of formula (XVII)
  • R is a halogen or a sulfonic acid ester group, e.g. bromine, iodine, mesylate, tosylate, triflate, phenylsulfonic acid ester, nitro-phenylsulfonic acid ester, or nonafluorobutylsulfonic acid ester, wherein the phenylsulfonic acid ester is optionally substituted by one or more groups independently selected from halogen, N0 2 , CN, d-C 4 alkyl, d-C 4 haloalkyl, d-C 4 alkoxy and CrC 4 haloalkoxy, for example tosylate or nitro- phenylsulfonic acid ester;
  • a halogen or a sulfonic acid ester group e.g. bromine, iodine, mesylate, tosylate, triflate, phenylsulfonic acid ester, nitro-
  • R 23 and R 24 independently of one another represent hydrogen, halogen, CN, Ci-C 4 alkyl, Ci-C 4 haloalkyl or phenyl, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-C 4 alkyl, d-C 4 haloalkyl, d-C 4 alkoxy and d-C 4 haloalkyoxy;
  • T 1 and T 2 independently of one another represent d-C 8 alkoxy, or T 1 and T 2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC 6 -alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C 6 alky;
  • D 1 , D 2 , Y 1 , Y 2 , Y 3 and R 1 are as defined herein for a compound of formula (I); or a salt or N-oxide thereof.
  • the preferred definitions of Y 1 , Y 2 , Y 3 and R 1 defined in respect of compounds of formula (I) also apply to compounds of formula (XVII).
  • the invention provides a compound of formula (XVI)
  • R represents hydrogen, halogen, CN, C 1 -C4 alkyl, C 1 -C4 haloalkyl or phenyl, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-d alkyl, d-d haloalkyl, Crd alkoxy and d-d haloalkoxy;
  • T 1 and T 2 independently of one another represent d-C 8 alkoxy, or T 1 and T 2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-Ci-C 6 -alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C 6 alkyl;
  • D 1 , D 2 , Y 1 , Y 2 , Y 3 and R 1 are as defined herein for compounds of formula (I); or a salt or N-oxide thereof.
  • the preferred definitions of Y 1 , Y 2 , Y 3 and R 1 defined in respect of compounds of formula (I) also apply to compounds of formula (XVI).
  • the invention provides a compound of formula (XVIII)
  • R 23 and R 24 independently of one another represent hydrogen, halogen, CN, C 1 -C4 alkyl, Ci- haloalkyl or phenyl, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, Crd alkyl, d-d haloalkyl, Crd alkoxy and Crd haloalkoxy;
  • T 1 and T 2 independently of one another represent d-C 8 alkoxy, or T 1 and T 2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC 6 -alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C 6 alkyl;
  • D 1 , D 2 , Y 1 , Y 2 , Y 3 and R 1 are as defined for a compound of formula (I); or a salt or N-oxide thereof.
  • the preferred definitions of Y 1 , Y 2 , Y 3 and R 1 defined in respect of compounds of formula (I) also apply to compounds of formula (XVIII).
  • the invention provides a compound of formula (XIX)
  • R represents CrC 4 alkyl
  • R 23 and R 24 independently of one another represent hydrogen, halogen, CN, Q-C 4 alkyl, Ci-C 4 haloalkyl or phenyl, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-C 4 alkyl, CrC 4 haloalkyl, d-C 4 alkoxy and CrC 4 haloalkoxy;
  • T 1 and T 2 independently of one another represent CrC 8 alkoxy, or T 1 and T 2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC 6 -alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C 6 alkyl;
  • D 1 , D 2 , Y 1 , Y 2 , Y 3 and R 1 are as defined for a compound of formula (I); or a salt or N-oxide thereof.
  • the preferred definitions of Y 1 , Y 2 , Y 3 and R 1 defined in respect of compounds of formula (I) also apply to compounds of formula (XIX).
  • the compounds of formula (I) may exist as different geometric or optical isomers or in different tautomeric forms. These may be separated and isolated by well-known (usually chromatographic) techniques, and all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms, such as deuterated compounds, are part of the present invention.
  • the carbon-nitrogen double bonds of the compound of formula (I) allow the four cis/trans isomers exemplified using compounds where A is A-l below:
  • the present invention includes each of these isomers.
  • the invention may provide a compound of formula (I) as just one of these isomers or as a mixture of one or more isomers in any ratio.
  • the invention also includes the corresponding isomers of the intermediates described herein, in particular compounds (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), (XII), (XIII), (XIV), (XV), (XVI), (XVII), (XVIII) and (XIX).
  • reaction scheme depicts synthesis of one geometric isomer
  • the scheme also includes synthesis of the other geometric isomers where possible.
  • reaction scheme A shown below encompasses reaction schemes B, C and D:
  • Table X represents Table 1 (when X is 1), Table 2 (when X is 2), Table 3 (when X is 3), Table 4 (when X is 4), Table 5 (when X is 5), Table 6 (when X is 6), Table 7 (when X is 7), Table 8 (when X is 8), Table 9 (when X is 9), Table 10 (when X is 10), Table 11 (when X is 11), Table 12 (when X is 12), Table 13 (when X is 13), Table 14 (when X is 14) and Table 10 15 (when X is 15).
  • A is A-l, wherein A 1 is A la
  • Table 1 This table discloses compounds 1.001 to 1.563 of the formula (I-I)
  • Table 7 This table discloses compounds 7.001 to 7.563 of the formula (I-VII)
  • Table 8 This table discloses compounds 8.001 to 8.563 of the formula (I-VIII)
  • Table 9 This table discloses compounds 9.001 to 9.563 of the formula (I-IX)
  • Table 11 This table discloses compounds 11.001 to 11.563 of the formula (I-XI)
  • Table 13 This table discloses compounds 13.001 to 13.563 of the formula (I-XIII)
  • Table 14 This table discloses compounds 14.001 to 14.563 of the formula (I-XIV)
  • Table 15 This table discloses compounds 15.001 to 15.563 of the formula (I-XV)
  • Table Y represents Table 16 (when Y is 16), Table 17 (when Y is 17), Table 18 (when Y is 18), Table 19 (when Y is 19), Table 20 (when Y is 20), Table 21 (when Y is 21), Table 22 (when Y is 22), Table 23 (when Y is 23), Table 24 (when Y is 24), Table 25 (when Y is 25), Table 26 (when Y is 26), Table 27 (when Y is 27), Table 28 (when Y is 28), Table 29 (when Y is 29), Table 30 (when Y is 30), and Table 31 (when Y is 31).
  • Table 16 This table discloses compounds 16.001 to 16.479 of the formula (I-XVI)
  • Table 17 This table discloses compounds 17.001 to 17.479 of the formula (I-XVII)
  • Table 18 This table discloses compounds 18.001 to 18.479 of the formula (I-XVIII)
  • Table 21 This table discloses compounds 21.001 to 21.479 of the formula (I-XXI)
  • Table 22 This table discloses compounds 22.001 to 22.479 of the formula (I-XXII)
  • Table 23 This table discloses compounds 23.001 to 23.479 of the formula (I-XXIII)
  • Table 24 This table discloses compounds 24.001 to 24.479 of the formula (I-XXIV)
  • Table 25 This table discloses compounds 25.001 to 25.479 of the formula (I-XXV)
  • Table 26 This table discloses compounds 26.001 to 26.4793 of the formula (I-XXVI)
  • Table 27 This table discloses compounds 27.001 to 27.479 of the formula (I-XXVII)
  • Table 28 This table discloses compounds 28.001 to 28.479 of the formula (I-XXVIII) (l-XXVIII)
  • Table 29 This table discloses compounds 29.001 to 29.479 of the formula (I-XXIX)
  • Table 30 This table discloses compounds 30.001 to 30.479 of the formula (I-XXX)
  • Table 31 This table discloses compounds 31.001 to 31.479 of the formula (I-XXXI)
  • Table Z represents Table 32 (when Z is 32), Table 33 (when Z is 33), Table 34 (when Z is 34)
  • Table 32 This table discloses compounds 32.001 to 32.043 of the formula (I-XXXII)
  • X represents -CH 2 -CH 2 -CH 2 - and A, Y 3 , G ⁇ G ⁇ G 3 , R 4 , R 5 , R 6 and R 7 have the specific meanings given in Table Z.
  • Table 33 This table discloses compounds 33.001 to 33.043 of the formula (I-XXXIII)
  • X represents -CH2-CH2-CH2- and A, Y 3 , G ⁇ G ⁇ G 3 , R 4 , R 5 , R 6 and R 7 have the specific meanings given in Table Z.
  • Table 34 This table discloses compounds 34.001 to 34.043 of the formula (I-XXXIV)
  • X represents -CH2-CH2-CH2- and A, Y 3 , G ⁇ G ⁇ G 3 , R 4 , R 5 , R 6 and R 7 have the specific meanings given in Table Z.
  • the compounds in Tables 1 to 34 include all isomers, tautomers and mixtures thereof, including the cis/trans isomers shown above.
  • the compounds of the invention may be made by a variety of methods, illustrated in schemes 1-12.
  • the compounds depicted in the schemes also indicate any isomers and tautomers, in particular the geometric isomers arising from the oxime and oxime ether moieties.
  • Compounds of formula (I) may be prepared by reacting a compound of formula (II) with a compound of formula (XX), wherein R 27 represents group A-6, A-7, A-8, A-9 or A- 5 10:
  • T 1 and T 2 are Q-C 8 alkoxy, or T 1 and T 2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC 6 -alkylidene-0) whereby the alkylidene fragment may optionally be mono- to tetra-substituted by CrC 6 alkyl 10 and D 1 , D 2 , R 3 , R 5 , R 6 and R 7 are as defined herein for compounds of formula (I), as seen in scheme 1.
  • compounds of formula (I) may be prepared by reacting a compound of formula (III), wherein D 1 , D 2 , A, X, and Y 3 and R 1 are as defined herein for compounds of formula (I) and T 1 and T 2 are CrC 8 alkoxy, or T 1 and T 2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC 6 -alkylidene-0) whereby the alkylidene fragment may optionally be mono- to tetra-substituted by Q-C 6 alkyl, and a compound of formula (XXI), wherein R 2 is as defined herein for compounds of formula (I) under conditions described in procedure 1.
  • compounds of formula (I) may be prepared by reacting a compound of formula (la), that is a compound of formula (I) wherein R 2 is hydrogen, and a compound of formula (XXII), wherein R 2 is as defined herein for compounds of formula (I) and R 25 is a halogen, in particular chlorine, bromine or iodine, or a sulfonic acid ester group, such as mesylate, tosylate, triflate, phenylsulfonic acid ester, nitro- phenylsulfonic acid ester, or nonafluorobutylsulfonic acid ester.
  • Oximes of formula (la) may be obtained by a condensation reaction, whereby a compound of formula (III) is reacted with hydroxylamine, or, alternatively, with a salt of hydroxylamine. A more detailed description of condensation reactions is given below.
  • compounds of formula (lb), that is a compound of formula (I) wherein X is X-3, X-4 or X-5, wherein Z 4 , Z 5 , Z 8 , Z 9 , Z 13 and Z 14 are methylene and Z 3 , Z 6 , Z 7 , Z 10 , Z 11 and Z 12 (represented in the scheme collectively as X') are as defined herein for compounds of formula (I), may be prepared by catalytic hydrogenation from compounds of formula (IV) in the presence of a metal catalyst, for example palladium, nickel or platinum. The reaction is usually carried out in the presence of a solvent under a hydrogen atmosphere. In some cases it is necessary to apply pressure in the range of 1 to 100 bar.
  • Suitable solvents for such reactions are alcohols, such as methanol or ethanol, cyclic ethers, such as dioxane or tetrahydrofuran or esters like ethyl acetate.
  • the reaction is usually carried out at a reaction temperature ranging from 0°C to the boiling point of the solvent.
  • a nickel catalyst can be found in Journal of Organometallic Chemistry, 333(2), 139-53; 1987.
  • Examples for the hydrogenation in the presence of a palladium catalyst can be found in Tetrahedron, 63(26), 6015-6034; 2007 or in Bioorganic & Medicinal Chemistry, 9(11), 2863-2870; 2001.
  • Examples for the hydrogenation in the presence of a platinum catalyst can be found in Journal of Organic Chemistry, 53(2), 386-90; 1988 or in Journal of Medicinal Chemistry, 32(8), 1820-35; 1989
  • one to five groups may be prepared by catalytic hydrogenation from compound (VI) in the presence of a metal catalyst like for example palladium, nickel or platinum.
  • the reaction is usually carried out in the presence of a solvent under a hydrogen atmosphere. In some cases it is necessary to apply pressure in the range of 1 to 100 bar.
  • Suitable solvents for such reactions are alcohols, such as methanol or ethanol, cyclic ethers, such as dioxane or tetrahydrofuran or esters like ethyl acetate.
  • the reaction is usually carried out at a reaction temperature ranging from 0°C to the boiling point of the solvent.
  • Examples for the hydrogenation in the presence of a nickel catalyst can be found in Journal of Organic Chemistry, 69(6), 1959-1966; 2004.
  • Examples for the hydrogenation in the presence of a palladium catalyst can be found in Journal of Organic Chemistry, 74(16), 6072-6076; 2009.
  • Examples for hydrogenation in the presence of a platinum catalyst can be found in Organometallics, 5(2), 348-55; 1986.
  • compounds of formula (Ic) may be obtained from compounds of formula (Illb), that is a compound of formula (III) wherein Z 3 , Z 6 , Z 7 , Z 10 , Z 11 and Z 12 are as defined herein for compounds of formula (I) (depicted in the scheme as X'); CHR 23 represents Z 4 , Z 8 or Z 13 ; CHR 24 represents Z 5 , Z 9 or Z 14 ; R 23 and R 24
  • phenyl independently of one another represent hydrogen, halogen, Ci- alkyl, Ci-d haloalkyl, phenyl or CN, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, Crd alkyl, Crd haloalkyl, Crd alkoxy and Crd haloalkyoxy.
  • the reaction can be carried out analogously to procedure 2 or procedures 3 and 4 as shown in Scheme 2.
  • the reaction can be carried out analogously to procedures procedure 2 or procedures 3 and 4 as shown in Scheme 2. In certain cases it may be appropriate to deprotect the ketone function first to obtain compounds of formula (XXIII) wherein X" represents
  • D 1 , D 2 , A, R 1 , R 17 , R 18 , Y 1 , Y 2 , Y 3 , Z 3 , Z 4 , Z 6 , Z 7 , Z 8 , Z 10 , Z 11 , Z 12 and Z 13 are as defined for a compound of formula (I).
  • Phosphorous ylides are usually prepared by treatment of a phosphonium salt with a base and phosphonium salts are usually prepared from a triarylphosphine and an alkyl halide.
  • Compounds of formula (IX) may be prepared from compounds of formula (X) by a Mitsunobu reaction.
  • the Mitsunobu reaction comprises the substitution of primary or secondary alcohols with nucleophiles, for example N-hydroxyphthalimide, as seen in
  • Compounds of formula (XXV) can be prepared from compounds of formula (XXIV), wherein D 1 , D 2 , X, Y 1 , Y 2 and Y 3 and R 1 are as defined herein for compounds of formula (I) and T 1 and T 2 are Q-C 8 alkoxy, or T 1 and T 2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC 6 -alkylidene-0)5 whereby the alkylidene fragment may optionally be mono- to tetra-substituted by CrC 6 alkyl.
  • Such transformations can be affected using a number of conditions well known to the person skilled in the art.
  • the reaction can be carried out in the presence of a palladium catalyst, for example tetrakis triphenyphosphine palladium (0) or dichlorobis (triphenylphosphine) palladium(II), a copper(I) salt like copper (I) chloride; copper (I) bromide or copper (I) iodide and a base, for example triethylamine, ethyldiisopropylamine, diethylamine, diisopropylamine or dicyclohexylamine. Where possible, the base may also serve as solvent.
  • a palladium catalyst for example tetrakis triphenyphosphine palladium (0) or dichlorobis (triphenylphosphine) palladium(II), a copper(I) salt like copper (I) chloride; copper (I) bromide or copper (I) iodide
  • a base for example triethylamine, ethyl
  • Examples for other suitable solvents are ⁇ , ⁇ -dimethylformamide, N,N-dimethylacetamide, acetonitrile, dimethylsulfoxide, dioxane or tetrahydrofuran.
  • the reaction is usually carried out at a reaction temperature ranging from 0°C to the boiling point of the solvent. Examples of Sonogashira reactions can be found in Handbook of Organopalladium Chemistry for Organic Synthesis 2002,1, 493-529.
  • Z 3 , Z 4 , Z 6 , Z 7 , Z 10 , Z 11 and Z 12 are as defined herein for a compound of formula (I);
  • R 25 is a halogen, in particular chlorine, bromine or iodine, or a sulfonic acid ester group, such as mesylate, tosylate, triflate, phenylsulfonic acid ester, nitro-phenylsulfonic acid ester, or nonafluorobutylsulfonic acid ester.
  • a halogen in particular chlorine, bromine or iodine
  • a sulfonic acid ester group such as mesylate, tosylate, triflate, phenylsulfonic acid ester, nitro-phenylsulfonic acid ester, or nonafluorobutylsulfonic acid ester.
  • Z 3 , Z 4 , Z 6 , Z 7 , Z 10 , Z 11 and Z 12 are as defined herein for a compound of formula (I);
  • Compounds of formula (XVIII) may be prepared from compounds of formula (XIX) by reduction with a metal hydride, for example lithium aluminium hydride or diisobutyl aluminium hydride. Examples for such reductions can found in Journal of Combinatorial Chemistry, 7(6), 958-967; 2005. The reaction is usually carried out at temperatures between -100 to 20°C in the presence of a solvent.
  • a metal hydride for example lithium aluminium hydride or diisobutyl aluminium hydride. Examples for such reductions can found in Journal of Combinatorial Chemistry, 7(6), 958-967; 2005.
  • the reaction is usually carried out at temperatures between -100 to 20°C in the presence of a solvent.
  • Appropriate bases are for example metal hydrides like calcium, lithium, sodium or potassium hydride, organometal compounds like buthyllithium or organic bases like for example triethylamine or ethyldiisopropylamine in combination with lithium chloride. Examples can be found in Bioorganic & Medicinal Chemistry, 11(18), 4015-4026; 2003; Synthesis, (4), 283-5; 1981 or in Journal of Medicinal Chemistry, 53(3), 1200-1210; 2010 Scheme 12:
  • Such a transformation may be performed by halogen metal exchange in compound (XXXIV) with an 10 appropriate reagent like for example magnesium, isopropyl magnesium chloride, or n- buthyllithium and the reaction of this metalated pyridine intermediate with a compound of formula (XXXIII) wherein X" represents
  • Compounds of formula (Hie) are especially useful as intermediates to a number of other compounds, wherein the hydroxy group formed is transformed into other functional groups, for example acid halides. Such transformations can be effected using a number of conditions well known to the person skilled in the art.
  • Compounds of formula (XXXIII) may be prepared by oxidation from compounds of formula (XXXII). Such oxidations can be affected using a number of conditions well known to the person skilled in the art. Specific reaction conditions may be found in Organic &
  • R 25 is a halogen, in particular chlorine, bromine or iodine, or a sulfonic acid ester group, such as mesylate, tosylate, triflate, phenylsulfonic acid ester, nitro-phenylsulfonic acid ester, or nonafluorobutylsulfonic acid ester.
  • a halogen in particular chlorine, bromine or iodine
  • a sulfonic acid ester group such as mesylate, tosylate, triflate, phenylsulfonic acid ester, nitro-phenylsulfonic acid ester, or nonafluorobutylsulfonic acid ester.
  • a sulfonic acid ester group such as mesylate, tosylate, triflate, phenylsulfonic acid ester, nitro-phenylsulfonic acid ester, or nonafluorobutylsulfonic acid
  • Oximes of formula (XXXV) may be obtained by a condensation reaction, whereby a compound of formula (XXa), that is a compound of formula XX wherein R 27 represents A-9 and T 1 and T 2 together with the carbon they are attached to form a carbonyl group is reacted with hydroxylamine, or, alternatively, with a salt of hydroxylamine.
  • a condensation reaction whereby a compound of formula (XXa), that is a compound of formula XX wherein R 27 represents A-9 and T 1 and T 2 together with the carbon they are attached to form a carbonyl group is reacted with hydroxylamine, or, alternatively, with a salt of hydroxylamine.
  • oximes of formula (XXXV) can be obtained by a nitrosation reaction of compounds of formula (XXXVI), wherein G 1 , G 2 , G 3 , p, R 4 , R 5 and R 6 are as defined herein for compounds of formula (I), with base and an alkyl nitrite, as seen in scheme 14.
  • Typical bases include lithium diisopropyl amide (LDA), lithium hexamethyldisilazane, n-butyl lithium, s-butyl lithium, tert-butyl lithium, sodium tert-butylate or potassium tert-butylate.
  • Typical alkyl nitrites include isopentyl nitrite and tert-butyl nitrite.
  • the compound of formula (XI), the alkyl nitrite or the base can be used in different stoichiometric amounts, with each reagent possibly being in excess with respect to the others.
  • such reactions are carried out under non-aqueous conditions in an inert solvent such as hexane, heptanes,
  • reaction may be performed at temperatures ranging from -80 to 250°C, preferably between -50 and 120°C.
  • Such reactions can lead to a mixture of the E- and the Z-oxime (ether) product, or the product may also be exclusively either the E- or the Z-oxime (ether).
  • Ketone intermediates of formula XXb that is a compound of formula XX wherein R 27 is A-10 and T 1 and T 2 together with the carbon they are attached to form a carbonyl group
  • XXc that is a compound of formula XX wherein R 27 is A-7 and T 1 and T 2 together with the carbon they are attached to form a carbonyl group
  • XXd that is a compound of formula XX wherein R 27 is A and T 1 and T 2 together with the carbon they are attached to form a carbonyl group -8 may be prepared by a variety of methods, illustrated in schemes 15-17.
  • Enolethers of formula (L) can be obtained by reacting enaminone of formula (LI) wherein G 1 , G 2 , G 3 , p, R 4 and R 5 are as defined herein for compounds of formula (I) and R 28 is alkyl with amidines or guanidines of formula (LII) wherein R 5 is a defined for compounds of formula (I).
  • condensation reactions can be performed using a number of conditions well known to the person skilled in the art. Such reactions are carried out in the presence of a base preferentially sodium or potassium alcoholate in ethanol or methanol. Specific reaction conditions may be found in Synthesis, 1012-1018, 1996; J. Heterocycl. Chem. 20, 649-653, 1983 or in WO2009010488.
  • Enaminone of formula (LI) can be obtained by reacting ketone of formula (LIII) wherein G 1 , G 2 , G 3 and p are as defined herein for compounds of formula (I) and R 28 is alkyl
  • Enol ether of formula (LIII) can be obtained by reacting ketones of formula (LVI) wherein G 1 , G 2 , G 3 and p are as defined herein for compounds of formula (I) with an alcohol of formula (LVII) wherein R 28 is alkyl. Such enol reactions can be affected using a number of
  • the reaction may be performed in the presence or absence of an inert organic or inorganic solvent, or in the presence of a mixture of such solvents. Preferentially, it is performed in the presence of one or more solvents.
  • Preferred solvents include the following aliphatic or aromatic hydrocarbons, which may optionally be substituted by one or more halogen atoms, such as pentane, hexanes, heptanes, cyclohexane, petroleum ether, benzene, toluene, xylene, chlorobenzene, dichlorobenzenes, dichloromethane, chloroform, 1,2-dichloroethane or carbon tetrachloride, ethers such as diethylether, diisopropyl ether, tert-butyl methyl ether, tetrahydrofuran, 1,4-dioxane, dimethoxyethane or diglycol dimethyl ether, ketones such as acetone
  • solvents includes water and alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, isopentanol, hexanol, trifluorethanol, ethylene glycol or methoxyethanol.
  • alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, isopentanol, hexanol, trifluorethanol, ethylene glycol or methoxyethanol.
  • the reaction may be performed between -20 C and 250 C, preferentially between 0 ° C and lOO C. In some cases the reaction mixture may be heated to reflux.
  • compounds can be used in the form of the free compound, or, alternatively, they can be used in the form of a salt such as the acetate, trifluoroacetate, propionate, benzoate, oxalate, methyl solfonate, phenylsulfonate, p-tolylsulfonate, trifluormethylsulfonate, fluoride, chloride, bromide, iodide, sulphate, hydrogensulphate or nitrate, including bis-salts if appropriate.
  • a salt such as the acetate, trifluoroacetate, propionate, benzoate, oxalate, methyl solfonate, phenylsulfonate, p-tolylsulfonate, trifluormethylsulfonate, fluoride, chloride, bromide, iodide, sulphate, hydrogensulphate or nitrate, including bis-salts if appropriate.
  • the reaction can be carried out in the absence of an acid using the free compounds. Alternatively, the reaction may be performed in the presence of an acid in catalytic, stoichiometric or excess amounts. Acids that could be used include acetic acid, propionic acid, oxalic acid, trifluoroacetic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, methansulfonic acid, para-toluenesulfonic acid, sulphuric acid, sodium hydrogensulphate and phosphoric acid.
  • the reaction can optionally be carried out in a water-free solvent system in the presence of a drying agent, such as sodium or magnesium sulphate, potassium carbonate or molecular sieves.
  • the condensation reaction can lead to a mixture of the E- and the Z-oxime (ether) product.
  • the condensation product may also be exclusively either the E- or the Z- oxime (ether).
  • Condensations can be performed under reduced pressure, normal pressure or increased pressure. Preferentially the reaction is performed under normal pressure.
  • the reaction may be performed in the absence or presence of a solvent or a mixture of solvents.
  • Preferential solvents include the following aliphatic or aromatic hydrocarbons that may optionally be substituted by one or more halogen atoms such as pentane, hexanes, heptanes, cyclohexane, petroleum ether, benzene, toluene, xylene, chlorobenzene, dichlorobenzenes, dichloromethane, chloroform, 1,2-dichloroethanev or carbon tetrachloride, ethers such as diethyl ether, diisopropyl ether, tert-butyl-methyl ether, tetrahydrofuran, 1,4- dioxane, dimethoxyethane or diglycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl
  • the selction of solvents includes also water and alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, isopentanol, hexanol, trifluorethanol, ethylene glycol or methoxyethanol.
  • alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, isopentanol, hexanol, trifluorethanol, ethylene glycol or methoxyethanol.
  • the reaction may be performed in a biphasic system comprising an organic solvent that is not miscible with water, such as toluene, dichloromethane, dichloro-ethylene, and an aqueous solvent, such as water.
  • a phase-transfer catalyst such as tetra-n-butylammonium bromide (TBAB)
  • TDMBAC Tetradecyldimethylbenzylammonium chloride
  • N-Benzyltrimethylammonium hydroxide N-Benzyltrimethylammonium hydroxide
  • the biphasic reaction may be performed with or without ultrasonication.
  • the reaction may be carried out at temperatures varying from -100°C and 250°C.
  • the temperature range is between 0°C and 100°C.
  • an organic or inorganic base may be present such as alkali- and earth alkali acetates, amides, carbonates, hydrogencarbonates, hydrides, hydroxides or alcoholates such as sodium, potassium, caesium or calcium acetate, sodium, potassium, caesium or calcium carbonate, sodium, potassium, caesium or calcium hydrogencarbonate, sodium, potassium, caesium or calcium hydride, sodium, potassium, caesium or calcium amide, sodium, potassium, caesium or calcium hydroxide, sodium, potassium, caesium or calcium
  • methanolate sodium, potassium, caesium or calcium ethanolate, sodium, potassium, caesium or calcium n-, i-, s- or t-butanolate, triethylamine, tri propylamine, tributylamine, di- isopropyl-ethylamine, ⁇ , ⁇ -dimethyl-cyclohexylamine, N-methyl-dicyclohexylamine, N,N- di methyl-aniline, N,N-diethyl-aniline, ⁇ , ⁇ -dimethyl-benzylamine, N,N-diethyl-benzylamine, pyridine, 2-methyl-pyridine, 3-methyl-pyridine, 4-methyl-pyridine, 2,6-dimethyl-pyridine, 2,4,6-trimethyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, N-ethyl-piperidine, N-methyl-morpholine, N-ethyl-morpholine,
  • the alkylation can be performed under reduced pressure, normal pressure or increased pressure. Preferentially the reaction is performed under normal pressure.
  • steps 1) to 31) may be required to be purified using, for example, chromatography, crystallisation or other purification techniques well known to the person skilled in the art.
  • the compounds of formula (I) to formula (XXXIV) and, where appropriate, the tautomers thereof, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
  • the invention therefore also relates to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a compound of formula (I) is applied as active ingredient to the plants, to parts thereof or the locus thereof.
  • the compounds of formula (I) according to the invention 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 useful plants.
  • the compounds of formula (I) can be used to inhibit or destroy the diseases 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 of formula (I) according to the 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 or in hygiene management.
  • the compounds of formula (I) are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes classes (e.g. Phytophthora, Pythium, Plasmopara).
  • Fungi imperfecti e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria
  • Basidiomycetes e.g. Rhizoctonia, Hemileia, Puccinia
  • useful plants 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
  • useful plants is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering.
  • herbicides like bromoxynil or classes of herbicides
  • EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors
  • GS glutamine synthetase
  • PPO protoporphyrinogen-oxidase
  • imazamox by conventional methods of breeding (mutagenesis) is Clearfield ® summer rape (Canola).
  • crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady ® , Herculex I ® and LibertyLink ® .
  • useful plants is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • YieldGard ® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm ® (maize variety that expresses a CrylllB(bl) toxin); YieldGard Plus ® (maize variety that expresses a CrylA(b) and a CrvIIIB(bl) toxin); Starlink ® (maize variety that expresses a Cry9(c) toxin); Herculex I ® (maize variety that expresses a CryIF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B ® (cotton variety that expresses a CrylA(c) toxin); Bollgard I ® (cotton variety that expresses a CrylA(c) toxin); Bollgard II
  • locus of a useful plant as used herein is intended to embrace the place on which the useful plants are growing, where the plant propagation materials of the useful plants are sown or where the plant propagation materials of the useful plants will be placed
  • An example for such a locus is a field, on which crop plants are growing.
  • plant propagation material is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants.
  • Plant propagation material is understood to denote seeds.
  • the compounds of formula (I) can be used in unmodified form or, preferably, together
  • the invention also relates to compositions for controlling and protecting against phytopathogenic microorganisms, comprising a compound of formula (I) and an inert carrier, and to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a composition, comprising a compound of formula (I) and an inert carrier, and to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a composition, comprising a compound of formula (I) and an inert carrier, and to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a composition, comprising a compound of formula (I) and an inert carrier, and to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a composition, comprising a compound of formula (I) and an inert carrier, and to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein
  • compositions of formula (I) and inert carriers 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.
  • the compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
  • Suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890.
  • the compounds of formula (I) or compositions, comprising a compound of formula (I) as active ingredient and an inert carrier can be applied to the locus of the plant or plant to be treated, simultaneously or in succession with further compounds.
  • further compounds can be e.g. fertilizers or micronutrient donors or other preparations which influence the growth of plants. They can also be selective herbicides 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.
  • a preferred method of applying a compound of formula (I), or a composition, comprising a compound of formula (I) as active ingredient and an inert carrier 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) may also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field.
  • the compounds of formula (I) may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
  • a formulation i.e. a composition comprising 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 When used as seed drenching agent, convenient rates of application are from lOmg to lg of active substance per kg of seeds.
  • the rate of application for the desired action can be determined by experiments. It depends for example on the type of action, the developmental stage of the useful plant, and on the application (location, timing, application method) and can, owing to these parameters, vary within wide limits.
  • the compounds of formula (I), or a pharmaceutical salt thereof, described above may also have an advantageous spectrum of activity for the treatment and/or prevention of microbial infection in an animal.
  • Animal can be any animal, for example, insect, mammal, reptile, fish, amphibian, preferably mammal, most preferably human.
  • Treatment means the use on an animal which has microbial infection in order to reduce or slow or stop the increase or spread of the infection, or to reduce the infection or to cure the infection.
  • Prevention means the use on an animal which has no apparent signs of microbial infection in order to prevent any future infection, or to reduce or slow the increase or spread of any future infection.
  • a compound of formula (I) in the manufacture of a medicament for use in the treatment and/or prevention of microbial infection in an animal.
  • a compound of formula (I) as a pharmaceutical agent.
  • a compound of formula (I) as an antimicrobial agent in the treatment of an animal.
  • a pharmaceutical composition comprising as an active ingredient a compound of formula (I), or a pharmaceutically acceptable salt thereof, and a
  • This composition can be used for the treatment and/or prevention of antimicrobial infection in an animal.
  • This pharmaceutical composition can be in a form suitable for oral administration, such as tablet, lozenges, hard capsules, aqueous suspensions, oily suspensions, emulsions dispersible powders, dispersible granules, syrups and elixirs.
  • this pharmaceutical composition can be in a form suitable for topical application, such as a spray, a cream or lotion.
  • this pharmaceutical composition can be in a form suitable for parenteral administration, for example injection.
  • this pharmaceutical composition can be in inhalable form, such as an aerosol spray.
  • the compounds of formula (I) may be effective against various microbial species able to cause a microbial infection in an animal.
  • microbial species are those causing Aspergillosis such as Aspergillus fumigatus, A. flavus, A. terrus, A. nidulans and A. niger, those causing Blastomycosis such as Blastomyces dermatitidis, those causing
  • Candidiasis such as Candida albicans, C. glabrata, C. tropicalis, C. parapsilosis, C. krusei and C. lusitaniae, those causing Coccidioidomycosis such as Coccidioides immitis, those causing Cryptococcosis such as Cryptococcus neoformans, those causing Histoplasmosis such as Histoplasma capsulatum and those causing Zygomycosis such as Absidia corymbifera, Rhizomucor pusillus and Rhizopus arrhizus.
  • Fusarium Spp such as Fusarium oxysporum and Fusarium solan/ and Scedosporium Spp such as Scedosporium apiospermum and Scedosporium prolificans.
  • Microsporum Spp Trichophyton Spp, Epidermophyton Spp, Mucor Spp, Sporothorix Spp, Phialophora Spp, Cladosporium Spp, Petriellidium spp, Paracoccidioides Spp and Histoplasma Spp.
  • biocidally active ingredients or compositions may be combined with the compound of formula (I) and used in the methods of the invention and applied simultaneously or sequentially with the compound of formula (I). When applied
  • these further active ingredients may be formulated together with the compound of formula (I) or mixed in, for example, the spray tank.
  • These further biocidally active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.
  • the present invention provides a composition comprising a compound of formula (I), which is selected from the Tables 1 to 34, and (i) a further fungicide, (ii) a herbicide, (iii) an insecticide, (iv) a bactericide, (v) an acaricide, (vi) a nematicide and/or (vii) a plant growth regulator.
  • the present invention provides for the use of a composition in the methods of the present invention, said composition comprising a compound of formula (I), which is selected from Tables 1 to 35, and (i) a further fungicide, (ii) a herbicide, (iii) an insecticide, (iv) a bactericide, (v) an acaricide, (vi) a nematicide and/or (vii) a plant growth regulator.
  • a composition comprising a compound of formula (I), which is selected from Tables 1 to 35, and (i) a further fungicide, (ii) a herbicide, (iii) an insecticide, (iv) a bactericide, (v) an acaricide, (vi) a nematicide and/or (vii) a plant growth regulator.
  • the compounds of the invention may also be applied with one or more systemically acquired resistance inducers ("SAR" inducer).
  • SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.
  • the present invention relates additionally to mixtures comprising at least a compound of formula I and at least a further, other biocidally active ingredient and optionally further ingredients.
  • the further, other biocidally active ingredient are known for example from "The Pesticide Manual” [The Pesticide Manual - A World Compendium; Thirteenth Edition (New edition (02 Nov 2003)); Editor: C. D. S. Tomlin; The British Crop Protection Council, ISBN-10: 1901396134; ISBN-13: 978-1901396133] or its electronic version "e-Pesticide Manual V4.2" or from the website http://www.alanwood.net/pesticides/ or preferably one of the further pesticides listed below.
  • TX means a compound encompassed by the compounds of formula I, or preferably the term “TX” refers to a compound selected from the Tables 1-34 and Tables 38-39:
  • an adjuvant selected from the group of substances consisting of petroleum oils
  • an acaricide selected from the group of substances consisting of l,l-bis(4-chloro- phenyl)-2-ethoxyethanol (IUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate (IUPAC/Chemical Abstracts name) (1059) + TX, 2-fluoro-N-methyl-N-l-naphthylacetamide (IUPAC name) (1295) + TX, 4-chlorophenyl phenyl sulfone (IUPAC name) (981) + TX, abamectin (1) + TX, acequinocyl (3) + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, alpha-cypermethrin (202) + TX, amidithion (870) + TX, amidoflumet [CCN]
  • bromopropylate (94) + TX, buprofezin (99) + TX, butocarboxim (103) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, calcium polysulfide (IUPAC name) (111) + TX, camphechlor (941) + TX, carbanolate (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbophenothion (947) + TX, CGA 50'439 (development code) (125) + TX, chinomethionat (126) + TX, chlorbenside (959) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorfenapyr (130) + TX, chlorfenethol (968) + TX, chlorfenson (970) + TX, chlorfensulphide (971) + TX, chlorfen
  • fenothiocarb (337) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fen- pyroximate (345) + TX, fenson (1157) + TX, fentrifanil (1161) + TX, fenvalerate (349) + TX, fipronil (354) + TX, fluacrypyrim (360) + TX, fluazuron (1166) + TX, flubenzimine (1167) + TX, flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1169) + TX, flufenoxuron (370) + TX, flumethrin (372) + TX, fluorbenside (1174) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, formetanate (405) + TX, forme
  • an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, crufomate (1011) + TX, doramectin (
  • an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX,
  • a bactericide selected from the group of substances consisting of 1-hydroxy-lH-pyridine- 2-thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodicin (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargaphen (alternative name)
  • a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX, Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis (alternative name) (33) + TX, Aphidius colemani (alternative name) (34) + TX, Aphidoletes aphidimyza (alternative name) (35) + TX, Autographa californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide (scientific name) (49) + TX, Bacillus thuringiensis Hopkins (scientific name) (5
  • Steinernema carpocapsae (alternative name) (742) + TX, Steinernema feltiae (alternative name) (742) + TX, Steinernema glaseri (alternative name) (742) + TX, Steinernema riobrave (alternative name) (742) + TX, Steinernema riobravis (alternative name) (742) + TX,
  • Steinernema scapterisci (alternative name) (742) + TX, Steinernema spp. (alternative name) (742) + TX, Trichogramma spp. (alternative name) (826) + TX, Typhlodromus occidentalis (alternative name) (844) and Verticillium lecanii (alternative name) (848) + TX,
  • a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537) + TX,
  • a chemosterilant selected from the group of substances consisting of apholate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholate [CCN] + TX, morzid [CCN] + TX, penfluron (alternative name) [CCN] + TX, tepa [CCN] + TX, thiohempa (alternative name) [CCN] + TX, thiotepa (alternative name) [CCN] + TX, tretamine
  • an insect pheromone selected from the group of substances consisting of (E)-dec-5-en- 1-yl acetate with (E)-dec-5-en-l-ol (IUPAC name) (222) + TX, (E)-tridec-4-en-l-yl acetate (IUPAC name) (829) + TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541) + TX, (E,Z)- tetradeca-4,10-dien-l-yl acetate (IUPAC name) (779) + TX, (Z)-dodec-7-en-l-yl acetate (IUPAC name) (285) + TX, (Z)-hexadec-ll-enal (IUPAC name) (436) + TX, (Z)-hexadec-ll- en-l-yl acetate (IUPAC name) (437) + TX, (Z)-hexadec-13
  • an insect repellent selected from the group of substances consisting of 2-(octylthio ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,
  • an insecticide selected from the group of substances consisting of 1-dichloro-l- nitroethane (IUPAC/Chemical Abstracts name) (1058) + TX, l,l-dichloro-2,2-bis(4- ethylphenyl)ethane (IUPAC name) (1056), + TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, l-bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916) + TX, 2,2,2- trichloro-l-(3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451) + TX, 2,2-dichlorovinyl 2- ethylsulphinylethyl methyl phosphate (IUPAC name) (1066) + T
  • chlorfenvinphos (131) + TX, chlorfluazuron (132) + TX, chlormephos (136) + TX, chloroform [CCN] + TX, chloropicrin (141) + TX, chlorphoxim (989) + TX, chlorprazophos (990) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, chromafenozide (150) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, cis-resmethrin (alternative name) + TX, cismethrin (80) + TX, clocythrin (alternative name) + TX, cloethocarb (999) + TX, closantel (alternative name) [CCN] + TX, cloth
  • flubendiamide (CAS. Reg. No.: 272451-65-7) + TX, flucofuron (1168) + TX, flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1169) + TX, flufenerim [CCN] + TX, flufenoxuron (370) + TX, flufenprox (1171) + TX, flumethrin (372) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, fonofos (1191) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1192) + TX, formparanate (1193) + TX, fosmethilan (1194) + TX, fospirate (1195) + TX, fosthiazate (408) + TX, fosthietan (1196) + TX,
  • naphthalene (IUPAC/Chemical Abstracts name) (1303) + TX, NC-170 (development code) (1306) + TX, NC-184 (compound code) + TX, nicotine (578) + TX, nicotine sulfate (578) + TX, nifluridide (1309) + TX, nitenpyram (579) + TX, nithiazine (1311) + TX, nitrilacarb (1313) + TX, nitrilacarb 1: 1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, nornicotine (traditional name) (1319) + TX, novaluron (585) + TX, noviflumuron (586) + TX, 0-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate (IUPAC name) (1057) +
  • a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (IUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + T
  • a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, l,2-dibromo-3-chloropropane (IUPAC/Chemical Abstracts name) (1045) + TX, 1,2-dichloropropane (IUPAC/ Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4- dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/Chemical Abstracts name) (1065) + TX, 3- (4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-l,3,5- thiadiazinan-3-ylacetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopur
  • a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX,
  • a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX,
  • a rodenticide selected from the group of substances consisting of 2-isovalerylindan-l,3- dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91) + TX, bromethalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorophacinone (140) + TX, cholecalciferol (alternative name) (850) + TX, coumachlor (1004) + TX, coumafuryl (
  • a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934) + TX, 5-(l,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX, an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX,
  • a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN] + TX,
  • a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX,
  • azaconazole 60207-31-0] + TX, bitertanol [70585-36-3] + TX, bromuconazole [116255-48-2] + TX, cyproconazole [94361-06-5] + TX, difenoconazole [119446-68-3] + TX, diniconazole [83657- 24-3] + TX, epoxiconazole [106325-08-0] + TX, fenbuconazole [114369-43-6] + TX, fluquinconazole [136426-54-5] + TX, flusilazole [85509-19-9] + TX, flutriafol [76674-21-0] + TX, hexaconazole [79983-71-4] + TX, imazalil [35554-44-0] + TX, imibenconazole [86598- 92-7] + TX,
  • composition stands for the various mixtures or combinations of components TX and (B), for example in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • the order of applying the components TX and (B) is not essential for working the present invention.
  • compositions according to the invention may also comprise more than one of the active components (B), if, for example, a broadening of the spectrum of disease control is desired. For instance, it may be advantageous in the agricultural practice to combine two or three components (B) with component TX.
  • An example is a composition comprising a compound of formula (I), azoxystrobin and cyproconazole.
  • the compound of the formula I is preferably a compound of Tables 1-34 and Tables 38-39, and more preferably, a compound selected from P.01, P.02, P.03, P.04, P.05, P.08, P.09, P.10, P.11, P.12, P.13, P.14, P.15, P.16, P.17, P.18, P.19, P.20, P.21, P.22, P.23A, P.24, P.29, P.33, P.34, P.
  • the mixing ratios can vary over a large range and are, preferably 100: 1 to 1:6000, especially 50: 1 to 1:50, more especially 20: 1 to 1:20, even more especially 10: 1 to 1: 10.
  • Those mixing ratios are understood to include, on the one hand, ratios by weight and also, on other hand, molar ratios.
  • mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient” relates to the respective mixture of TX with the mixing partner).
  • Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type.
  • other formulation types may be prepared.
  • one active ingredient is a water insoluble solid and the other a water insoluble liquid
  • the resultant composition is a suspoemulsion (SE) formulation.
  • compositions wherein component TX and component (B) are present in the composition in amounts producing a synergistic effect.
  • This synergistic activity is apparent from the fact that the fungicidal activity of the composition comprising component TX and component (B) is greater than the sum of the fungicidal activities of component TX and of component (B).
  • This synergistic activity extends the range of action of component TX and component (B) in two ways.
  • the expected (additive) action of active ingredients A)+B) using p+q ppm of active ingredient is 1 uu
  • synergism corresponds to a positive value for the difference of (O-E).
  • expected activity said difference (O-E) is zero.
  • a negative value of said difference (O-E) signals a loss of activity compared to the expected activity.
  • compositions according to the invention can also have further surprising advantageous properties.
  • advantageous properties are: more advantageuos degradability; improved toxicological and/or ecotoxicological behaviour; or improved characteristics of the useful plants including: emergence, crop yields, more developed root system, tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf colour, less fertilizers needed, less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, improved plant vigor, and early germination.
  • compositions according to the invention have a systemic action and can be used as foliar, soil and seed treatment fungicides.
  • compositions according to the invention it is possible to inhibit or destroy the phytopathogenic microorganisms which occur in plants or in parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different useful plants, while at the same time the parts of plants which grow later are also protected from attack by phytopathogenic microorganisms.
  • the compositions according to the invention can be applied to the phytopathogenic microorganisms, the useful plants, the locus thereof, the propagation material thereof, storage goods or technical materials threatened by microorganism attack.
  • compositions according to the invention may be applied before or after infection of the useful plants, the propagation material thereof, storage goods or technical materials by the microorganisms.
  • a further aspect of the present invention is a method of controlling diseases on useful plants or on propagation material thereof caused by phytopathogens, which comprises applying to the useful plants, the locus thereof or propagation material thereof a composition according to the invention.
  • a method which comprises applying to the useful plants or to the locus thereof a composition according to the invention, more preferably to the useful plants.
  • a method which comprises applying to the
  • compositions according to the invention may also comprise more than one of the active components (B), if, for example, a broadening of the spectrum of disease control is desired. For instance, it may be advantageous in the agricultural practice to combine two or three components (B) with component TX.
  • An example is a composition comprising a compound of formula (I), azoxystrobin and cyproconazole.
  • the isomer drawn is in excess in the reaction mixture and/or product
  • Methane sulfonyl chloride (118mg) was added at 0-5°C to a solution of triethylamine (0.21ml_) and (E)-l-[6-(3-hydroxy-prop-l-ynyl)-pyridin-2-yl]-ethanone O-methyl-oxime (150mg) in dichloromethane (3.0ml_). After stirring for lOmin at 5°C and 90min at ambient temperature sodium bicarbonate (10% w/w aqueous solution; lmL) was added and the reaction mixture was diluted with dichloromethane, washed with water and brine and dried over sodium sulfate.
  • Methane sulfonyl chloride (0.498g) was added at 0-5°C to a solution of (E)-2-methyl-3- [6-(2-methyl-[l,3]dioxolan-2-yl)-pyridin-2-yl]-prop-2-en-l-ol (0.93g) and triethylamine (1.09g) in dichloromethane (15ml_). After stirring for 2h at 0-5°C sodium bicarbonate (2ml_, 20% aqueous solution) was added.
  • Diisobutyl aluminium hydride (1M in dichloromethane; 12.4ml_) was added within 30min at -60°C to a solution of 2-methyl-3-[6-(2-methyl-[l,3]dioxolan-2-yl)-pyridin-2-yl]-acrylic acid ethyl ester (1.69g) in dichloromethane (30ml_). After stirring for 3h at -60°C the cooling bath was removed and water (0.5ml_), NaOH (2M aqueous solution; 0.5ml_) and again water (lmL) were added. During these additions the temperature raised to 10°C.
  • 6-Bromo-pyridine-2-carbaldehyde (2.5g) and (E)-l-(6-methyl-pyridin-2-yl)-ethanone O-prop- 2-ynyl-oxime (2.53g) were dissolved in THF (80ml_).
  • Diisopropylamine (3.79mL), dichlorobis (tri phenyl phospine) palladium (II) (283mg) and copper (I) iodide (205mg) were added. After stirring for 6h at ambient temperature the reaction mixture was diluted with ethyl acetate washed with sodium bicarbonate (10% aqueous solution), water and brine.
  • Butyl lithium (1.6M in hexane; 1.27ml_) was added at -70°C to a solution of
  • N-hydroxyphthalimide (6.4g) and triphenylphosphine (11.3g) were added portion wise at 5°C to a solution of (E)-l-[6-(3-Hydroxy-prop-l-ynyl)-pyridin-2-yl]-ethanone O-methyl-oxime (8.0g) in tetrahydrofuran (60ml_).
  • hydrazine monohydrate (0.23 mL) was added dropwise to a suspension of 2-[3-(6- ⁇ l-[(E)-methoxyimino]-ethyl ⁇ -pyridin-2-yl)-prop- 2-ynyloxy]-isoindole-l,3-dione (810 mg) in ethanol (5 mL). After stirring for 4 h at ambient temperature the reaction mixture was poured on water and then NaOH (4M aqueous solution) was added until the pH was 14. The basic solution was extracted twice with ethyl acetate.

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Abstract

The present invention provides compounds of formula (I) wherein R1, R2, A, X, D1, D2 and Y3 are as defined in the claims. The invention further provides intermediates used in the preparation of these compounds, to compositions which comprise these compounds and to their use in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.

Description

Novel Microbiocides
The present invention relates to novel microbiocidally active, in particular fungicidally active, oxime derivatives. It further relates to intermediates used in the preparation of these compounds, to compositions which comprise these compounds and to their use in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.
Fungicidally active bisoximes are described in WO08074418.
Surprisingly, it has been found that novel oxime derivatives have microbiocidal activity.
The present invention accordingly relates to bisoxime derivatives of formula (I)
Figure imgf000003_0001
wherein
R1 represents hydrogen, halogen, CN, SH, Ci-C8 alkylthio, Ci-C8 alkylsulphinyl, Ci-C8 alkylsulphonyl, NH2, Ci-Cio alkyl, C3-C8 cycloalkyl, C2-C8 alkenyl, C2-C8 alkynyl,
(R80)carbonyl(Ci-C4 alkyl), phenyl or pyridyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, NH-CrC8 alkyl, N(CrC8 alkyl)2, N02, OR8, CrC alkyl, CrC haloalkyl, C3-C6 cycloalkyl and a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms;
R2 represents hydrogen, Ci-C8 alkyl, C3-C8 cycloalkyl, C3-C8 alkenyl, C3-C8 alkynyl, benzyl, phenyl or pyridyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, CrC alkyl, CrC haloalkyl, CrC alkoxy and CrC haloalkoxy;
D1 represents N or C-Y1;
D2 represents N or C-Y2;
wherein both D1 and D2 cannot be N;
A represents group A-l, A-2, or A-3:
Figure imgf000004_0001
A-1 A-2 A-3
Wherein A1 represents the cycle Ala, Al , or Alc:
Figure imgf000004_0002
R3 represents hydrogen, halogen, CN, SH, Ci-C8 alkylthio, Ci-C8 alkylsulphinyl, Ci-C8 alkylsulphonyl, NH2, Ci-Cio alkyl, C3-C8 cycloalkyl, C2-C8 alkenyl, C2-C8 alkynyl,
(R80)carbonyl(Ci-C4 alkyl), phenyl or pyridyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, NH-CrC8 alkyl, N(CrC8 alkyl)2, N02, OR8, d-C alkyl, d-C haloalkyl, C3-C6 cycloalkyl and a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms;
R4, R5, R6 and R7 independently of one another represent hydrogen, halogen, CN, N02, Ci-C8 alkyl, C3-C8 cycloalkyl, C2-C8 alkenyl, C2-C8 alkynyl, phenyl, a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, COR9, OR8, SH, Ci-C8-alkylthio, Ci-C8- alkylsulphinyl, Ci-C8-alkylsulphonyl, phenylthio, phenylsulphinyl, phenylsulphonyl, N(R10)2, C02R8, 0(CO)R9, CON(R10)2, NR10COR9 or CR9N-OR8, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, phenyl and heterocycle are optionally substituted by one or more groups
independently selected from halogen, CN, NH2, N02, OR8, CrC alkyl and CrC haloalkyl; or, when A is A-1, wherein A1 is Ala or Al , or when A is A-2, R5 and R6, R6 and R4, or R7 and R4 together with the fragment of the ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a partially or fully unsaturated 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from O, S, N and N(R10), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, and wherein the ring formed by R5 and R6, R6 and R4, or R7 and R4 is optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, C1-C4 alkyl, C1-C4 haloalkyi, C1-C4 alkoxy and C1-C4 haloalkoxy;
G1 and G2 independently of one another represent -C(R12R13)-;
G3 represents -C(R12R13)-, O, N(R14) or S;
or G1 and G2, or G2 and G3, or G1 and G1 together represent -CR12=CR13-;
each R12 and R13 independently of one another represent hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyi, C1-C4 alkoxy or C1-C4 haloalkoxy;
R14 represents hydrogen, OH, C1-C4 alkyl, d-d alkoxy, C3-C6 cycloalkyl, C d alkylcarbonyl or Ci-C8 haloalkylcarbonyl;
p represents 0, 1 or 2;
X represents X-2, X-3, X-4 or X-5:
#—∑—∑—# #— Z— Z— Z— # #— Z— Z— Z— Z— #
X-2 X-3 X-4
#_z!2_z _z!2_ z!3_z!i_#
X-5
Z1, Z2, Z3, Z5, Z6, Z7, Z8, Z9, Z10, Z11, Z13 and Z14 independently of one another represent CR15R16, C=0 or C=CR17R18;
Z4 and Z12 represent CR19R20, SiR21R22, C=0 or C=CR17R18;
each R15 and R16 independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl, d-d haloalkyi or phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, Crd alkyl, d-d haloalkyi, Crd alkoxy and Crd haloalkoxy;
or R15 and R16 together with the carbon atom to which they are attached may form a
C3-C6 cycloalkyl group or a C3-C6 halocycloalkyl group;
each R17 and R18 independently of one another represent hydrogen, halogen, Crd alkyl or -d haloalkyi;
each R19, R20, R21 and R22 independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl, C1-C4 haloalkyi or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, d-d alkyl, d- haloalkyi, C d alkoxy and Crd haloalkoxy;
or R19 and R20 together with the carbon atom to which they are attached may form a C3-C6 cycloalkyl group or a C3-C6 halocycloalkyl group;
wherein the groupings X-2, X-3, X-4 and X-5 contain at most one ring which contains either only one of the radicals Z1 to Z14 or two radicals Z1 to Z14 or three radicals Z1 to Z14 or four radicals Z1 to Z14 as ring members; wherein radicals Z1, Z3, Z6 and Z10 are not substituted by OH; and wherein none of Z1, Z2, Z3, Z4, Z5, Z6, Z7, Z8, Z9, Z10, Z11, Z12, Z13 and Z14 represent a carbon atom substituted by two OH;
Y1, Y2 and Y3 independently of one another represent hydrogen, halogen, CN, N02, Ci-Cs alkyl, C3-C8 cycloalkyi, C2-C8 alkenyl, C2-C8 alkynyl, phenyl, a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, COR9, OR8, SH, Ci-C8-alkylthio, d-C8- alkylsulphinyl, Ci-C8-alkylsulphonyl, phenylthio, phenylsulphinyl, phenylsulphonyl, N(R10)2, C02R8, 0(CO)R9, CON(R10)2, NR10COR9 or CR9N-OR8, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl, and heterocycle are optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OR8, d-d alkyl and d-d haloalkyl; or Y1 and Y3, or Y2 and Y3 together with the fragment of the pyridyl ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a partially or fully unsaturated 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from O, S, N and N(R10), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, and wherein the ring formed by Y1 and Y3, or Y2 and Y3 is optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, d-d alkyl, Crd haloalkyl, Crd alkoxy and Crd haloalkoxy;
each R8 independently of one another represents hydrogen, d-C8 alkyl, C3-C8 cycloalkyi, C3-C8 alkenyl, C3-C8 alkynyl, phenyl, benzyl or a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl, benzyl and heterocycle are optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, CrC alkyl, CrC -haloalkyl, CrC alkoxy, CrC haloalkoxy, and Crd-alkoxy-Crd-alkyl;
each R9 independently of one another represents hydrogen, d-C8 alkyl, C3-C8 cycloalkyi, C2-C8 alkenyl, C2-C8 alkynyl, phenyl, benzyl or pyridyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, Crd alkyl, Crd haloalkyl, Crd alkoxy and d-C4 haloalkoxy;
each R10 independently of one another represents hydrogen, OH, d-C8 alkyl, d-C8 alkoxy, CrC8-alkoxy-CrC4-alkyl, C3-C8 alkenyl, C3-C8 alkynyl, or COR9, wherein the alkyl, alkoxy, alkenyl and alkynyl are optionally substituted by one or more halogen; wherein when two radicals R are attached to the same nitrogen atom, these radicals can be identical or different;
wherein when two radicals R10 are attached to the same nitrogen atom, both of these radicals cannot be OH, d-d alkoxy or d-d haloalkoxy;
and wherein when two radicals R10 are attached to the same nitrogen atom, these two radicals together with the nitrogen atom to which they are attached may form a cycle B- 1, B-2, B-3, B-4, B-5, B-6, B-7 or B-8:
Figure imgf000007_0001
wherein the cycle formed is optionally substituted by one or more groups
independently selected from halogen, CN, NH2, N02, OH, d-d alkyl, d-d haloalkyi, d-d alkoxy and d-d haloalkoxy;
or a salt or an N-oxide thereof.
The invention covers all agronomically acceptable salts, isomers, structural isomers, stereoisomers, diastereoisomers, enantiomers, tautomers, atropisomers and N-oxides of those compounds. The compounds of formula I may exist in different geometric or optical isomeric forms or in different tautomeric forms. One or more centres of chirality may be present, in which case compounds of the formula I may be present as pure enantiomers, mixtures of enantiomers, pure diastereomers or mixtures of diastereomers. There may be double bonds present in the molecule, such as C=C or C=N bonds, in which case compounds of formula I may exist as single isomers or mixtures of isomers. Centres of tautomerisation may be present. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds. Also
atropisomerism may occur as a result of a restricted rotation about a single bond.
Halogen, either as a lone substituent or in combination with another substituent (e.g. haloalkyi) is generally fluorine, chlorine, bromine or iodine, and usually fluorine, chlorine or bromine.
Each alkyl moiety (including the alkyl moiety of alkoxy, alkylthio, etc.) is a straight or branched chain and, depending on the number of carbon atoms it contains, is, for example, methyl, ethyl, ^propyl, -butyl, 7-pentyl, ^-hexyl, /so-propyl, sec-butyl, /so-butyl, te i-butyl, 7eopentyl, -heptyl or 1,3-dimethylbutyl, and usually methyl or ethyl. The alkenyl and alkynyl groups can be mono- or di -unsaturated and are examples thereof are derived from the above mentioned alkyl groups.
Haloalkyl moieties are alkyl moieties which are substituted by one or more of the same or different halogen atoms and are, for example, monofluoromethyl, difluoromethyl, thfluoromethyl, monochloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2,2- difluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl, 1-fluoroethyl, 2-chloroethyl, pentafluoroethyl, l,l-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl, and typically trichloromethyl, difluorochloromethyl, difluoromethyl, thfluoromethyl and
dichlorofluoromethyl.
Alkoxy is, for example, methoxy, ethoxy, propoxy, /so-propoxy, -butoxy, /so-butoxy, sec-butoxy and te i-butoxy, and usually methoxy or ethoxy.
Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2- trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy, and usually difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.
Alkylthio is, for example, methylthio, ethylthio, propylthio, /so-propylthio, ^-butylthio,
/so-butylthio, sec-butylthio or te f-butylthio, and usually methylthio or ethylthio.
Alkylsulphonyl is, for example, methylsulphonyl, ethylsulphonyl, propylsulphonyl, iso- propylsulphonyl, ^-butylsulphonyl, /so-butylsulphonyl, sec-butylsulphonyl or tert- butylsulphonyl, and usually methylsulphonyl or ethylsulphonyl.
Alkylsulphinyl is, for example, methylsulphinyl, ethylsulphinyl, propylsulphinyl, iso- propylsulphinyl, ^-butylsulphinyl, /so-butylsulphinyl, sar-butylsulphinyl or te i-butylsulphinyl, and usually methylsulphinyl or ethylsulphinyl.
Cycloalkyl may be saturated or partially unsaturated, preferably fully saturated, and is, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl,
ethoxyethyl, -propoxymethyl, 7-propoxyethyl, /so-propoxymethyl or /so-propoxyethyl.
Aryl includes phenyl, naphthyl, anthracyl, fluorenyl and indanyl, but is usually phenyl. Carbocycle includes cycloalkyl groups and aryl groups.
Heterocycloalkyl is a non-aromatic ring that may be saturated or partially
unsaturated, preferably fully saturated, containing carbon atoms as ring members and at least one heteroatom selected from O, S and N as ring members. Examples include oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, 1,3-dioxolanyl, 1,4-dioxanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, oxazinanyl, morpholinyl, thiomorpholinyl, imidazolidinyl, pyrazolidinyl and piperazinyl, preferably morpholinyl, pyrrolidinyl, piperdinyl and piperazinyl, more preferably morpholinyl and pyrollidinyl. Heteroaryl is, for example, a monovalent monocyclic or bicyclic aromatic hydrocarbon radical. Examples of monocyclic groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, and thiadiazolyl. Samples of bicyclic groups include quinolinyl, cinnolinyl, quinoxalinyl, benzimidazolyl, benzothiophenyl, and benzothiadiazolyl. Monocyclic heteroaryl groups are preferred, preferably pyridyl, pyrrolyl, imidazolyl and triazolyl, e.g. 1,2,4 triazolyl, pyridyl and imidazolyl being most preferred.
The terms "heterocycle" and "heterocyclic ring" are used interchangeably and are defined to include heterocycloalkyl and heteroaryl groups. Any reference herein to a heterocycle or heterocyclic ring preferably refers to the specific examples given under the definition of heteroaryl and heterocycloalkyl above, and are preferably morpholinyl, pyrrolidinyl, piperdinyl, piperazinyl pyridyl, pyrrolyl, imidazolyl and triazolyl, e.g. 1,2,4 triazolyl, more preferably morpholinyl, pyrollidinyl, pyridyl and imidazolyl.
Where a moiety is indicated as being (optionally) substituted, e.g. alkyi, this includes those moieties where they are part of a larger group, e.g. the alkyi in the alkylthio group. The same applies, e.g. to the phenyl moiety in phenylthio etc. Where a moiety is indicated as being optionally substituted by one or more other groups, preferably there are one to five optional substituents, more preferably one to three optional substituents. Where a moiety is substituted by a cyclic group, e.g. aryl, heteroaryl, cycloalkyi, preferably there are no more than two such substituents, more preferably no more than one such substituent.
The following substituents definitions, including preferred definitions, may be combined in any combination:
R1 represents hydrogen, halogen, CN, SH, d-C8 alkylthio, d-C8 alkylsulphinyl, d-C8 alkylsulphonyl, NH2, d-Cio alkyi/ C3-C8 cycloalkyi, C2-C8 alkenyl, C2-C8 alkynyl,
(R80)carbonyl(Crd alkyi), phenyl or pyridyl, wherein the alkyi, cycloalkyi, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, NH-CrC8 alkyi, N(CrC8 alkyl)2, N02, OR8, CrC4 alkyi, CrC4 haloalkyl, C3-C6 cycloalkyi and a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms.
Preferably, R1 represents hydrogen, d-C8 alkyi, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyi, phenyl, pyridyl, or (R80)carbonyl(d-C4 alkyi), wherein the alkyi, alkenyl, alkynyl, cycloalkyi, phenyl and pyridyl are optionally substituted by one or more groups
independently selected from halogen, CN, OR8, NH2, NH-CrC8 alkyi, N(CrC8 alkyl)2, CrC4 alkyi, d-C4 haloalkyl, C3-C6 cycloalkyi and pyridyl. More preferably, R1 represents hydrogen, Ci-C4 alkyl, C2-C4 alkenyl, phenyl or pyridyl, wherein the alkyl, alkenyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, OH, NH2, NH-Ci-C4 alkyl, N(Ci-C4 alkyl)2, C1-C4 alkyl, Ci-C4 haloalkyl, Ci-C4 alkoxy, Ci-C4 haloalkoxy and C3-C6 cycloalkyi.
Even more preferably, R1 represents hydrogen, CrC4 alkyl, Ci-C4 haloalkyl, phenyl or pyridin-2-yl, wherein the phenyl and pyridin-2-yl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy.
In one group of compounds, R1 represents Ci-C4 alkyl, C2-C4 alkenyl, phenyl or pyridyl, wherein the alkyl, alkenyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, Ci-C4 alkoxy and Ci-C4 haloalkoxy.
In another group of compounds, R1 represents hydrogen, d-C4 alkyl, d-C4 haloalkyl and phenyl, wherein the phenyl is optionally substituted by one or more groups
independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy.
In this group of compounds, preferably, R1 represents hydrogen, d-C4 alkyl or phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy.
More preferably in this group, R1 represents hydrogen, d-C4 alkyl or phenyl.
R2 represents hydrogen, d-C8 alkyl, C3-C8 cycloalkyi, C3-C8 alkenyl, C3-C8 alkynyl, benzyl, phenyl or pyridyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, CrC alkyl, CrC haloalkyl, CrC alkoxy and CrC haloalkoxy.
Preferably, R2 represents hydrogen, d-C8 alkyl, d-C8 haloalkyl, C3-C8 cycloalkyi, C3-C8 halocycloalkyl, C3-C8 alkenyl, C3-C8 haloalkenyl, C3-C8 alkynyl, C3-C8 haloalkynyl, benzyl or pyridyl, wherein the benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, d-C4 alkyl, d-C4 haloalkyl, d-C4 alkoxy and d-C4 haloalkoxy.
More preferably, R2 represents d-C4 alkyl, C3-C6 alkenyl, C3-C6 alkynyl or benzyl, wherein the alkyl, alkenyl, alkynyl and benzyl are optionally substituted by one or more groups independently selected from halogen, CN, d-C4 alkoxy and d-C4 haloalkoxy.
Even more preferably, R2 represents hydrogen, d-C8 alkyl, or d-C8 haloalkyl.
In one group of compounds R2 represents hydrogen, d-C4 alkyl, C3-C6 alkenyl, C3-C6 alkynyl or benzyl, wherein the alkyl, alkenyl, alkynyl and benzyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from d-C4 alkyl, d-C4 haloalkyl, halogen, CN, d-C4 alkoxy and d-C4 haloalkoxy. In another group of compounds, R2 represents hydrogen, Ci-C4 alkyl, C3-C6 alkenyl or C3-C5 alkynyl, wherein the alkyl, alkenyl, or alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, Ci-C4 alkoxy and Ci-C4 haloalkoxy.
In this group, preferably R2 represents hydrogen, Ci-C4 alkyl, C3-C6 alkenyl or C3-C6 alkynyl, wherein the alkyl, alkenyl, or alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy.
More preferably in this group of compounds, R2 represents hydrogen, Ci-C4 alkyl, Cs- Ce alkenyl or C3-C6 alkynyl.
In one group of compounds, D1 is C-Y1 and D2 is C-Y2.
In another group of compounds, D1 is C-Y1 and D2 is N.
In a further group of compounds, D1 is N and D2 is C-Y2.
Preferably D1 is C-Y1 and D2 is C-Y2, and more preferably, D1 and D2 are CH.
R3 represents hydrogen, halogen, CN, SH, d-C8 alkylthio, CrC8 alkylsulphinyl, d-C8 alkylsulphonyl, NH2, C1-C10 alkyl, C3-C8 cycloalkyl, C2-C8 alkenyl, C2-C8 alkynyl,
(R90)carbonyl(d-C4 alkyl), phenyl or pyridyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, NH2, NH-d-C8 alkyl, N(d-C8 alkyl)2, N02, OR8, d-C4 alkyl, d-C4 haloalkyl, C3-C6 cycloalkyl and a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms. The heterocycle is preferably one as defined herein, preferably morpholinyl, pyrrolidinyl, piperdinyl, piperazinyl, pyridyl, pyrrolyl, imidazolyl or triazolyl, e.g. 1,2,4 triazolyl, more preferably morpholinyl, pyrollidinyl, pyridyl or imidazolyl.
Preferably, R3 represents hydrogen, d-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, phenyl, pyridyl or (R80)carbonyl(d-C4 alkyl), wherein the alkyl, alkenyl, alkynyl, cycloalkyl, phenyl and pyridyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, OR8, NH2, NH-d-Qs alkyl, N(CrC8 alkyl)2, d-C4 alkyl, d-C4 haloalkyl, C3-C6 cycloalkyl and pyridyl.
More preferably, R3 represents hydrogen, d-C4 alkyl, C2-C4 alkenyl, phenyl or pyridyl, wherein the alkyl, alkenyl, phenyl and pyridyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, OH, NH2, NH-Cr C alkyl, N(CrC alkyl)2, CrC alkyl, CrC haloalkyl, CrC alkoxy, CrC haloalkoxy and C3-C6 cycloalkyl.
In one preferred group of compounds, R3 represents d-d alkyl, C2-C4 alkenyl, phenyl or pyridyl, wherein the alkyl, alkenyl, phenyl and pyridyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-d alkoxy and Crd haloalkoxy.
In another preferred group of compounds, R3 represents hydrogen, d-d alkyl, d-d haloalkyl, phenyl or pyridin-2-yl, wherein the phenyl and pyridin-2-yl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy.
In another group of compounds, R3 represents hydrogen, CN, d-d alkyl, C3-C6 cycloalkyi, C2-d alkenyl, C2-d alkynyl, (Ci-dalkoxy)carbonyl(Ci-d alkyl), phenyl or pyridyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, NH-Ci-C8 alkyl, N(d-C8 alkyl)2, N02, OH, d-d alkyl, d-d haloalkyl, C3-C6 cycloalkyi, pyridyl or pyrroline
In this group of compounds, preferably R3 represents hydrogen, CN, Crd alkyl, C2-C4 alkenyl, C2-C4 alkynyl or phenyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, NH-Crd alkyl, N(CrC4 alkyl)2, OH, CrC4 alkyl, CrC4 haloalkyl, C3-C6 cycloalkyi, pyridyl or pyrroline.
More preferably in this group of compounds, R3 represents hydrogen, Crd alkyl, phenyl, wherein the alkyl and phenyl pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, NH-Crd alkyl, N(d-C4 alkyl)2, OH, Crd alkyl, Crd haloalkyl, C3-C6 cycloalkyi or pyrroline.
A represents group A-l, A-2, or A-3.
Preferably A represents group A-l, wherein A1 represents Ala or A-l represents A-2. In one group of compounds, A represents group A-l. Preferably in this group, A1 represents cycle Ala.
In another group of compounds, A represents cycle A-2 or A-3. Preferably in this group, A represents cycle A-2.
R4, R5, R6 and R7 independently of one another represent hydrogen, halogen, CN, N02, d-C8 alkyl, C3-C8 cycloalkyi, C2-C8 alkenyl, C2-C8 alkynyl, phenyl, a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms (e.g. a heterocycle as defined herein, preferably morpholinyl, pyrrolidinyl, piperdinyl, piperazinyl, pyridyl, pyrrolyl, imidazolyl or triazolyl, e.g. 1,2,4 triazolyl, more preferably morpholinyl, pyrollidinyl, pyridyl or imidazolyl), COR9, OR8, SH, Ci-C8-alkylthio, CrC8-alkylsulphinyl, CrC8-alkylsulphonyl, phenylthio, phenylsulphinyl, phenylsulphonyl, N(R10)2, C02R8, 0(CO)R9, CON(R10)2, NR10COR9 or CR9N- OR8, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl and heterocycle are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, NH2, N02, OR8, d-C alkyl, d-C haloalkyl;
or, when A is A-l, wherein A1 is Ala or Al , or when A is A-2, R5 and R6, R6 and R4, or R7 and R4 together with the fragment of the ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a partially or fully unsaturated 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from O, S, N and N(R10), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, and wherein the ring formed by R5 and R6, R6 and R4, or R7 and R4 is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, NH2, N02, OH, CrC alkyl, d-C haloalkyl, CrC alkoxy and CrC haloalkoxy. Preferably, R4, R5, R6 and R7 independently of one another represent hydrogen, halogen, CN, OR8, Ci-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyi, phenyl, pyridyl, N(R10)2, C02R8, NR10COR9, SH, CrC8-alkylthio, Ci-C8-alkylsulphinyl, CrC8-alkylsulphonyl, phenylthio, phenylsulphinyl or phenylsulphonyl, wherein the alkyl, alkenyl, cycloalkyi, phenyl and pyridyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, OR8, Q-C, alkyl and Q-C, haloalkyl;
or when A is A-l, wherein A1 is Ala or Al or A-2, R5 and R6, R6 and R4, or R4 and R7, together with the fragment of the pyridyl ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a partially or fully unsaturated 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from O, S, N and N(R10), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, wherein the ring formed by R5 and R6, R6 and R4, or R4 and R7 is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-C4 alkyl, d-C4 haloalkyl, d-C4 alkoxy and CrC4 haloalkoxy;
More preferably, R4, R5, R6 and R7 independently of one another represent hydrogen, halogen, OR8, CN, Q-C4 alkyl, C3-C6 cycloalkyi, N(R10)2, phenyl, C02R8 or NR10COR9, wherein the alkyl, cycloalkyi and phenyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-C4 alkyl, CrC4-haloalkyl, d-C4 alkoxy and d-C4 haloalkoxy;
or, when A is A-l, wherein A1 is Ala or Al or A-2, R5 and R6, R6 and R4, or R4 and R7, together with the fragment of the pyridyl ring to which they are attached may form a fully or partially unsaturated 5- or 6-membered carbocyclic ring optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, methyl and halomethyl. More preferably, R4, R5, R6 and R7 independently of one another represent hydrogen, halogen, OH, CN, C1-C4 alkyl, C1-C4 alkoxy, C3-C6 alkenyloxy, C3-C6 cycloalkyl, N(R10)2, phenyl or C02R8, wherein the alkyl, alkoxy, alkenyloxy, cycloalkyl and phenyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, C1-C4 alkyl, Ci-C4-haloalkyl, Ci-C4 alkoxy and C1-C4 haloalkoxy;
or, when A is A-l, wherein A1 is Ala or Al , or when A is A-2, R5 and R6, R6 and R4, or R4 and R7, together with the fragment of the pyridyl ring to which they are attached may form a fully or partially unsaturated 6-membered carbocyclic ring optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, methyl and halomethyl.
More preferably, R4, R5, R6 and R7 independently of one another represent hydrogen, halogen, OH, CN, Q-C, alkyl, Q-C, alkoxy, C3-C6 alkenyloxy, C3-C6 cycloalkyl, N(R10)2, phenyl or C02R8, wherein the alkyl, alkoxy, alkenyloxy, cycloalkyl and phenyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-C4 alkyl, CrC4-haloalkyl, d-C4 alkoxy and CrC4 haloalkoxy.
More preferably, R4, R5, R6 and R7 independently of one another represent hydrogen, C1-C4 alkyl, CN or d-C4 alkoxy, wherein the alkyl and alkoxy are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-C4 alkoxy and d-C4 haloalkoxy.
In another group of compounds, R5 represents hydrogen, d-C4 alkyl, d-C4 haloalkyl,
OH, d-C4 alkoxy, d-C4 haloalkoxy, phenyl or pyridyl, wherein the phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, Ci-C4 alkyl, CrC4 haloalkyl, CrC4 alkoxy and CrC4 haloalkoxy.
In a further group of compounds, R4 and R6 independently of one another represent hydrogen, CN, OR8, NH2, halogen, CrC8 alkyl, CrC8 haloalkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, SH, CrC8 alkylthio, N(R10)2, NR10COR9, phenyl or pyridyl, wherein phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, methyl, CN, methoxy, halomethyl and halomethoxy;
each R8 independently represents one another represents hydrogen, d-C8 alkyl, C3-C8 cycloalkyl, C3-C8 alkenyl, C3-C8 alkynyl, benzyl, phenyl or pyridyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, d-C4 alkyl, d-C4- haloalkyl, d-C4 alkoxy, d-C4 haloalkoxy and d-C4-alkoxy-CrC4-alkyl;
each R9 independently of one another represents d-C4-alkyl or d-C4 haloalkyl;
each R10 independently of one another represent hydrogen or d-C4 alkyl; wherein when two radicals R are attached to the same nitrogen atom, these radicals can be identical or different;
and wherein when two radicals R10 are attached to the same nitrogen atom, these two radicals together with the nitrogen atom to which they are attached may form a cycle B- 1, B-2, B-3, B-4 or B-5, wherein the cycle formed is optionally substituted by one or more groups independently selected from halogen, methyl and halomethyl.
In yet another group of compounds, R4 and R6 independently of one another represent hydrogen, CN, OH, NH2, halogen, Ci-C4 alkyl, Ci-C4 haloalkyl, Ci-C4 alkoxy, Ci-C4 haloalkoxy, C3-C6 cycloalkyi, N(R10)2, NR10COR9 or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, methyl, CN, methoxy, halomethyl and halomethoxy;
each R9 independently represents CrC4-alkyl or d-C4 haloalkyl;
each R10 independently of one another represent hydrogen or d-C4 alkyl;
wherein when two radicals R10 are attached to the same nitrogen atom, these radicals can be identical or different;
and wherein when two radicals R10 are attached to the same nitrogen atom, these two radicals together with the nitrogen atom to which they are attached may form a cycle B- 1, B-2, B-3, B-4 or B-5, wherein the cycle formed is optionally substituted by one or more groups independently selected from halogen, methyl and halomethyl.
In another group of compounds, R4 represents hydrogen, halogen, CN, d-C6 alkyl,
C3-C6 cycloalkyi, C2-C6 alkenyl, C2-C6 alkynyl, phenyl, OH, Q-C, alkoxy, NH2, NH(CrC alkyl), N(d-C4 alkyl)2, CO(Ci-C4 alkyl), wherein the alkyl, cycloalkyi, alkenyl, alkynyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy.
Preferably in this group of compounds, R4 represents hydrogen, halogen, CN, d-C6 alkyl, C3-C6 cycloalkyi, C2-C4 alkenyl, C2-C4 alkynyl, phenyl, d-C4 alkoxy or CO(d-C4 alkyl), wherein the alkyl, cycloalkyi, alkenyl, alkynyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy.
More preferably in this group of compounds, R4 represents hydrogen, halogen, CN,
Ci-C alkyl, CrC alkoxy, CrC haloalkyl, C3-C6 cycloalkyi, CO(CrC alkyl).
G1 and G2 independently of one another represent -C(R12R13)-;
G3 represents -C(R12R13)-, O, N(R14) or S;
or G1 and G2, or G2 and G3, or G1 and G1 together represent -CR12=CR13-.
Each R12 and R13 independently of one another represent hydrogen, halogen, d-C4 alkyl, d-C4 haloalkyl, d-C4 alkoxy or d-C4 haloalkoxy. R represents hydrogen, OH, d-d alkyl, d-d alkoxy, C3-C6 cycloalkyl, d- alkylcarbonyl or d- haloalkylcarbonyl.
Preferably, G1 and G2 independently of one another represent -C(R12R13)-;
G3 represents -C(R12R13)-, O, N(R14) or S;
each R12 and R13 independently of one another represent hydrogen, halogen, d-d alkyl, d-d haloalkyl, d-d alkoxy or d-d haloalkoxy;
R14 represents hydrogen, OH, d-d alkyl, d-d alkoxy, C3-C6 cycloalkyl, d-d alkylcarbonyl or d-d haloalkylcarbonyl.
Preferably, G1, G2 and G3 represent C(R3 )2, wherein each R34 independently of one another represents hydrogen or d-d alkyl.
In another group of compounds, G1 represents -CH2-;
G2 represents -C(R12R13)-;
G3 represents -C(R12R13)-, O, N(R14) or S;
each R12 and R13 independently of one another represent hydrogen or d- a'kyl; R14 represents hydrogen or d- p represents 0, 1 or 2. Preferably, p is 1 or 2. More preferably, p is 1.
X represents X-2, X-3, X-4 or X-5.
Preferably X represents X-3 or X-5.
More preferably X represents X-3.
Z1, Z2, Z3, Z5, Z6, Z7, Z8, Z9, Z10, Z11, Z13 and Z14 independently of one another represent CR15R16, C=0 or C=CR17R18, preferably CR15R16 or C=CR17R18.
Z4 and Z12 represent CR19R20, SiR21R22, C=0 or C=CR17R18; preferably CR19R20 or C=CR17R18. In one group of compounds, Z4 is preferably CR19R20.
When X is X-2 preferably one of Z1 and Z2 is methylene or halomethylene, preferably methylene.
When X is X-3, preferably two of Z3, Z4 and Z5 are independently methylene or halomethylene, preferably methylene. Preferably Z3 and Z5 are methylene or halomethylene, preferably methylene.
When X is X-4, preferably three of Z6, Z7, Z8 and Z9 are independently methylene or halomethylene, preferably methylene.
When X is X-5, preferably four of Z10, Z11, Z12, Z13 and Z14 are independently methylene or halomethylene, preferably methylene. Preferably Z10, Z11, Z13 and Z14 are independently methylene or halomethylene, preferably methylene.
Wherein radicals Z1, Z3, Z6 and Z10 are not substituted by OH; and none of Z1, Z2, Z3, Z4, Z5, Z6, Z7, Z8, Z9, Z10, Z11, Z12, Z13 and Z14 represent a carbon atom substituted by two OH groups. Each R and R independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl, C1-C4 haloalkyl or phenyl, wherein the phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy;
or R15 and R16 together with the carbon atom to which they are attached may form a
C3-C6 cycloalkyl group or a C3-C6 halocycloalkyl group.
Preferably, each R15 and R16 independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl or C1-C4 haloalkyl.
Each R17 and R18 independently of one another represent hydrogen, halogen, C1-C4 alkyl or C1-C4 haloalkyl.
Preferably, each R17 and R18 independently of one another represent hydrogen, halogen, methyl or halomethyl.
Each R19 and R20 independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl, Q-C4 haloalkyl or phenyl, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-C4 alkyl, C1-C4 haloalkyl, d-C4 alkoxy and Q-C4 haloalkoxy;
or R19 and R20 together with the carbon atom to which they are attached may form a C3-C6 cycloalkyl group or a C3-C6 halocycloalkyl group.
Preferably, each R19 and R20 independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl, C1-C4 haloalkyl or phenyl, wherein the phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
or R19 and R20 together with the carbon atom to which they are attached may form a C3-C6 cycloalkyl group or a C3-C6 halocycloalkyl group.
Each R21 and R22 independently of one another represent hydrogen, halogen, CN, OH,
C1-C4 alkyl, Q-C4 haloalkyl or phenyl, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-C4 alkyl, C1-C4 haloalkyl, d-C4 alkoxy and Q-C4 haloalkoxy.
Preferably, each R21 and R22 independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl, Q-C4 haloalkyl or phenyl, wherein the phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy.
More preferably, each R21 and R22 independently of one another represent halogen, C1-C4 alkyl, Q-C4 haloalkyl or phenyl, wherein the phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy. Y1, Y2 and Υ3 independently of one another represent hydrogen, halogen, CN, N02, Ci-Cs alkyl, C3-C8 cycloalkyi, C2-C8 alkenyl, C2-C8 alkynyl, phenyl, a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms (e.g. a heterocycle as defined herein, preferably morpholinyl, pyrrolidinyl, piperdinyl, piperazinyl, pyridyl, pyrrolyl, imidazolyl or triazolyl, e.g. 1,2,4 triazolyl, more preferably morpholinyl, pyrollidinyl, pyridyl or imidazolyl), COR9, OR8, SH, Ci-Cs-alkylthio, Ci-C8-alkylsulphinyl, Ci-C8-alkylsulphonyl, phenylthio, phenylsulphinyl, phenylsulphonyl, N(R10)2, C02R8, 0(CO)R9, CON(R10)2, NR10COR9 or CR9N- OR8, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl and heterocycle are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, NH2, N02, OR8, Q-G, alkyl and Q-G, haloalkyl;
or Y1 and Y3, or Y2 and Y3 together with the fragment of the pyridyl ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a partially or fully unsaturated 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from O, S, N and N(R10), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms and wherein the ring formed by Y1 and Y3, or Y2 and Y3 is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, NH2, N02, OH, Q-G, alkyl, Q-G, haloalkyl, Q-G, alkoxy and Q-G, haloalkoxy.
Preferably, Y1, Y2 and Y3 independently of one another represent hydrogen, halogen, CN, OR8, G-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyi, phenyl, pyridyl, N(R10)2, C02R8,
NR10COR9, SH, Ci-C8-alkylthio, CrC8-alkylsulphinyl, CrC8-alkylsulphonyl, phenylthio, phenylsulphinyl or phenylsulphonyl, wherein the alkyl, alkenyl, cycloalkyi, phenyl and pyridyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, OR8, CrC4 alkyl and CrC4 haloalkyl.
More preferably Y1, Y2 and Y3 independently of one another represent hydrogen, halogen, OR8, CN, Q-C4 alkyl, C3-C6 cycloalkyi, N(R10)2, phenyl, C02R8 or NR10COR9, wherein the alkyl, cycloalkyi and phenyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, G-C4 alkyl, CrC4-haloalkyl, G-C4 alkoxy and CrC4 haloalkoxy.
More preferably, Y1, Y2, and Y3 independently of one another represent hydrogen, halogen, OH, CN, Q-G, alkyl, Q-G, alkoxy, C3-C6 alkenyloxy, C3-C6 cycloalkyi, N(R10)2, phenyl or C02R8, wherein the alkyl, alkoxy, alkenyloxy, cycloalkyi and phenyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, G-C4 alkyl, G-C4-haloalkyl, G-C4 alkoxy and CrC4 haloalkoxy. More preferably Y1, Y2 and Y3 independently of one another represent hydrogen, d- C4 alkyi, CN or C1-C4 alkoxy, wherein the alkyi and alkoxy are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, Ci-C4 alkoxy and C1-C4 haloalkoxy.
In one group of compounds Y1 and Y2 independently of one another represent hydrogen, C1-C4 alkyi, CN or Ci-C4 alkoxy, wherein the alkyi and alkoxy are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, Ci-C4 alkoxy and Ci-C4 haloalkoxy and Y3 is as defined according to any of the defintions above.
In another group of compounds, Y1 and Y2 each represent H;
Y3 represents hydrogen, halogen, CN, Ci-C4 alkyi, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl or d-C4 alkoxy wherein the alkyi, cycloalkyl, alkenyl and alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, C1-C4 alkyi and Q-C, haloalkyl.
Preferably in this group of compounds, Y1 and Y2 each represent H;
Y3 represents hydrogen, halogen, CN, Ci-C4 alkyi, C2-C6 alkenyl, C2-C6 alkynyl or d-C4 alkoxy wherein the alkyi, cycloalkyl, alkenyl and alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, d-C4 alkyi and d-C4 haloalkyl.
Even more preferably in this group of compounds, Y1 and Y2 each represent H;
Y3 represents hydrogen, methyl, methoxy, methoxymethyl, wherein the methyl, methoxy, methoxymethyl are optionally substituted by one or more halogen.
Each R8 independently of one another represents hydrogen, d-C8 alkyi, C3-C8 cycloalkyl, C3-C8 alkenyl, C3-C8 alkynyl, phenyl, benzyl or a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, wherein the alkyi, cycloalkyl, alkenyl, alkynyl, phenyl, benzyl and heterocycle are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, NH2, N02, OH, d-C4 alkyi, d-C4-haloalkyl, d-C4 alkoxy, d-C4 haloalkoxy and d-C4-alkoxy-CrC4-alkyl. The heterocycle is preferably one as defined herein, preferably morpholinyl, pyrrolidinyl, piperdinyl, piperazinyl, pyridyl, pyrrolyl, imidazolyl or triazolyl, e.g. 1,2,4 triazolyl, more preferably morpholinyl, pyrollidinyl, pyridyl or imidazolyl.
Preferably, each R8 independently of one another represents hydrogen, d-C8 alkyi, d-C8 haloalkyl, C3-C8 alkenyl, C3-C8 haloalkenyl, C3-C8 haloalkynyl, phenyl, benzyl or pyridyl, wherein the phenyl, benzyl and pyridyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, NH2, N02, OH, d-d alkyl, d-d-haloalkyl, d-d alkoxy and d-d haloalkoxy.
More preferably, each R8 independently of one another represents hydrogen, Ci-Cs alkyl, Ci-Cs haloalkyl, C3-C8 alkenyl, C3-C8 haloalkenyl, C3-C8 alkynyl, C3-C8 haloalkynyl, phenyl, benzyl, or pyridyl, wherein the phenyl, benzyl and pyridyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-d alkyl, d-d-haloalkyl, d-d alkoxy and d-d haloalkoxy.
More preferably, each R8 independently of one another represents hydrogen, d-d alkyl or d-d haloalkyl.
In one group of compounds, each R8 independently of one another represents hydrogen, Ci-C8 alkyl, C3-C8 cycloalkyi, C3-C8 alkenyl, C3-C8 alkynyl, phenyl, benzyl or pyridyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, d-d alkyl, d-d-haloalkyl, d-d alkoxy, d-d haloalkoxy and Crd-alkoxy-Crd-alkyl.
Preferably in this group of compounds, each R8 independently of one another represents hydrogen, Crd alkyl, C3-C6 alkenyl, C3-C6 alkynyl, phenyl or benzyl.
Each R9 independently of one another represents hydrogen, d-C8 alkyl, C3-C8 cycloalkyi, C2-C8 alkenyl, C2-C8 alkynyl, phenyl, benzyl or pyridyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl, benzyl and pyridyl are optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, NH2, N02, OH, d-d alkyl, Crd haloalkyl, Cr alkoxy and Crd haloalkoxy.
Preferably, each R9 independently of one another represents hydrogen, d-C8 alkyl or Ci-C8 haloalkyl.
More preferably each R9 independently of one another represents hydrogen, Cr alkyl or Crd haloalkyl.
Each R10 independently of one another represents hydrogen, OH, d-C8 alkyl, d-C8 alkoxy, CrC8-alkoxy-Crd-alkyl, C3-C8 alkenyl, C3-C8 alkynyl, or COR9, wherein the alkyl, alkoxy, alkenyl and alkynyl are optionally substituted by one or more halogen; wherein when two radicals R10 are attached to the same nitrogen atom, these radicals can be identical or different; wherein when two radicals R10 are attached to the same nitrogen atom, both of these radicals cannot be OH, Cr alkoxy or Crd haloalkoxy; and wherein when two radicals R10 are attached to the same nitrogen atom, these two radicals together with the nitrogen atom to which they are attached may form a cycle B-l, B-2, B-3, B-4, B-5, B-6, B-7 or B-8:
Figure imgf000021_0001
B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 wherein the cycle formed is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, NH2, N02, OH, d-d alkyl, d-d haloalkyi, d-d alkoxy and d-d haloalkoxy.
Preferably, each R10 independently of one another represents hydrogen, d-C8 alkyl or
COR9; wherein when two radicals R10 are attached to the same nitrogen atom, these radicals can be identical or different; and wherein when two radicals R10 are attached to the same nitrogen atom, these two radicals together with the nitrogen atom to which they are attached may form a cycle B-1, B-2, B-3, B-4 or B-5 wherein the cycle formed is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, methyl and halomethyl.
More preferably, each R10 independently of one another represents hydrogen or d-d alkyl; wherein when two radicals R10 are attached to the same nitrogen atom, these radicals can be identical or different; and wherein when two radicals R10 are attached to the same nitrogen atom, these two radicals together with the nitrogen atom to which they are attached may form a cycle B-1, B-2, B-3, B-4 or B-5 wherein the cycle formed is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, methyl and halomethyl.
In one preferred group of compounds:
R1 represents hydrogen, d-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyi, phenyl, pyridyl or (R80)carbonyl(d-C4 alkyl), wherein the alkyl, alkenyl, alkynyl, cycloalkyi, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, OR8, NH2, NH-CrC8 alkyl, N(CrC8 alkyl)2, CrC4 alkyl, CrC4 haloalkyi, C3-C6 cycloalkyi and pyridyl;
R2 represents hydrogen, d-C8 alkyl, d-C8 haloalkyi, C3-C8 cycloalkyi, C3-C8 halocycloalkyl, C3-C8 alkenyl, C3-C8 haloalkenyl, C3-C8 alkynyl, C3-C8 haloalkynyl, benzyl or pyridyl, wherein the benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, Crd alkyl, d-C4 haloalkyi, Crd alkoxy and d-C4 haloalkoxy;
R3 represents hydrogen, d-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyi, phenyl, pyridyl, or (R80)carbonyl(d-C4 alkyl), wherein the alkyl, alkenyl, alkynyl, cycloalkyi, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, OR8, NH2, NH-Ci-C8 alkyl, N(d-C8 alkyl)2, d-C alkyl, d-C haloalkyl, C3-C6 cycloalkyl and pyridyl;
A represents group A-l, A-2, or A-3;
R4, R5, R6 and R7 independently of one another represent hydrogen, halogen, CN,
OR8, Ci-Cs alkyl, C2-C8 alkenyl, C3-C8 cycloalkyl, phenyl, pyridyl, N(R10)2, C02R8, NR10COR9, SH, Ci-Cs-alkylthio, Ci-C8-alkylsulphinyl, Ci-C8-alkylsulphonyl, phenylthio, phenylsulphinyl or phenylsulphonyl, wherein the alkyl, alkenyl, cycloalkyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, OR8, Ci-C4 alkyl and d-C4 haloalkyl;
or, when A is A-l, wherein A1 is Ala or Al , or when A is A-2, R5 and R6, R6 and R4, or R4 and R7, together with the fragment of the pyridyl ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a partially or fully unsaturated 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from O, S, N and N(R10), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, wherein the ring formed by R5 and R6, R6 and R4, or R4 and R7 is optionally substituted by one or more groups independently selected from halogen, CN, d-C4 alkyl, Q- C4 haloalkyl, d-C4 alkoxy and CrC4 haloalkoxy;
X represents X-3 or X-5;
Z3, Z5, Z10, Z11, Z13 and Z14 independently of one another represent CR15R16 or C=CR17R18;
Z4 and Z12 represent CR19R20 or C=CR17R18;
each R15 and R16 independently of one another represent hydrogen, halogen, CN, OH, Ci-C, alkyl or Q-C, haloalkyl;
each R17 and R18 independently of one another represent hydrogen, halogen, d-C4 alkyl or d-C4 haloalkyl;
each R19 and R20 independently of one another represent hydrogen, halogen, CN, OH, d-C4 alkyl, d-C4 haloalkyl or phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
or R19 and R20 together with the carbon atom to which they are attached may form a C3-C6 cycloalkyl group or a C3-C6 halocycloalkyl group;
Y1, Y2 and Y3 independently of one another represent hydrogen, halogen, CN, OR8, Ci-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyl, phenyl, pyridyl, N(R10)2, C02R8, NR10COR9, SH, Q- C8-alkylthio, CrC8-alkylsulphinyl, d-C8-a I kyl sulphonyl, phenylthio, phenylsulphinyl or phenylsulphonyl, wherein the alkyl, alkenyl, cycloalkyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, OR8, d-d alkyl and Crd haloalkyl;
each R8 independently of one another represents hydrogen, d-C8 alkyl, d-C8 haloalkyl, C3-C8 alkenyl, C3-C8 haloalkenyl, C3-C8 haloalkynyl, phenyl, benzyl or pyridyl, wherein the phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, d-d alkyl, d-d-haloalkyl, d-d alkoxy and d-d haloalkoxy;
each R9 independently of one another represents hydrogen, Ci-C8 alkyl or Ci-C8 haloalkyl;
each R10 independently of one another represents hydrogen, Ci-C8 alkyl or COR9; wherein when two radicals R10 are attached to the same nitrogen atom, these radicals can be identical or different;
and wherein when two radicals R10 are attached to the same nitrogen atom, these two radicals together with the nitrogen atom to which they are attached may form a cycle B- 1, B-2, B-3, B-4 or B-5 wherein the cycle formed is optionally substituted by one or more groups independently selected from halogen, methyl and halomethyl.
In a more preferred group of compounds:
R1 represents hydrogen, Crd alkyl, C2-C4 alkenyl, phenyl or pyridyl, wherein the alkyl, alkenyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, OH, NH2, NH-CrC4 alkyl, N(CrC4 alkyl)2, CrC4 alkyl, Crd haloalkyl, Crd alkoxy, Crd haloalkoxy and C3-C6 cycloalkyl;
R2 represents d-C4 alkyl, C3-C6 alkenyl, C3-C6 alkynyl or benzyl, wherein the alkyl, alkenyl, alkynyl and benzyl are optionally substituted by one or more groups independently selected from halogen, CN, Crd alkoxy and Crd haloalkoxy;
R3 represents hydrogen, Crd alkyl, C2-C4 alkenyl, phenyl or pyridyl, wherein the alkyl, alkenyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, OH, NH2, NH-CrC4 alkyl, N(CrC4 alkyl)2, CrC4 alkyl, d-C4 haloalkyl, Crd alkoxy, Crd haloalkoxy and C3-C6 cycloalkyl;
A represents group A-l, A-2, or A-3;
R4, R5, R6 and R7 independently of one another represent hydrogen, halogen, OR8, CN, d-d alkyl, C3-C6 cycloalkyl, N(R10)2, phenyl, C02R8 or NR10COR9, wherein the alkyl, cycloalkyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, Crd alkyl, d-C4-haloalkyl, Crd alkoxy and d-C4 haloalkoxy; or, when A is A-l, wherein A1 is Ala or Al , or when A is A-2, R5 and R6, R6 and R4, or
R4 and R7, together with the fragment of the pyridyl ring to which they are attached may form a fully or partially unsaturated 5- or 6-membered carbocyclic ring, optionally substituted by one or more groups independently selected from halogen, methyl and halomethyl;
X represents X-3;
Z3 and Z5 independently of one another represent CR15R16 or C=CR17R18;
Z4 represents CR19R20 or C=CR17R18;
each R15 and R16 independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl or C1-C4 haloalkyi;
each R17 and R18 independently of one another represent hydrogen, halogen, C1-C4 alkyl or C1-C4 haloalkyi;
each R19 and R20 independently of one another represent hydrogen, halogen, CN, OH,
C1-C4 alkyl, C1-C4 haloalkyi or phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
or R19 and R20 together with the carbon atom to which they are attached may form a C3-C6 cycloalkyl group or a C3-C6 halocycloalkyl group;
wherein at least two of Z3, Z4 and Z5 are methylene;
Y1, Y2 and Y3 independently of one another represent hydrogen, halogen, OR8, CN, C1-C4 alkyl, C3-C6 cycloalkyl, N(R10)2, phenyl, C02R8 or NR10COR9 wherein the alkyl, cycloalkyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, d-C4 alkyl, CrC4-haloalkyl, d-C4 alkoxy and CrC4 haloalkoxy;
each R8 independently of one another represents hydrogen, d-C8 alkyl, d-C8 haloalkyi, C3-C8 alkenyl, C3-C8 haloalkenyl, C3-C8 alkynyl, C3-C8 haloalkynyl, phenyl, benzyl, or pyridyl, wherein the phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, d-C4 alkyl, d-C4-haloalkyl, d-C4 alkoxy and d-C4 haloalkoxy;
each R9 independently of one another represents hydrogen, d-C4 alkyl or d-C4 haloalkyi;
each R10 independently of one another represents hydrogen or d-C4 alkyl;
wherein when two radicals R10 are attached to the same nitrogen atom, these radicals can be identical or different;
and wherein when two radicals R10 are attached to the same nitrogen atom, these two radicals together with the nitrogen atom to which they are attached may form a cycle B- 1, B-2, B-3, B-4 or B-5 wherein the cycle formed is optionally substituted by one or more groups independently selected from halogen, methyl and halomethyl.
In another group of compounds: R1 represents hydrogen, C1-C4 alkyl, C1-C4 haloalkyi, phenyl or pyridin-2-yl, wherein the phenyl and pyridin-2-yl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
R2 represents hydrogen, Ci-C8 alkyl, or Ci-C8 haloalkyi; R3 represents hydrogen, d-d alkyl, d-d haloalkyi, phenyl or pyridin-2-yl, wherein the phenyl and pyridin-2-yl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
A represents group A-l, A-2 or A-3;
R4, R5, R6 and R7 independently of one another represent hydrogen, halogen, OH, CN, Ci-d alkyl, Crd alkoxy, C3-C6 alkenyloxy, C3-C6 cycloalkyi, N(R10)2, phenyl or C02R8, wherein the alkyl, alkoxy, alkenyloxy, cycloalkyi and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, Crd alkyl, d-C4-haloalkyl, Ci- alkoxy and d-d haloalkoxy;
X represents X-3;
Z3 and Z5 independently of one another represent CR15R16 or C=CR17R18;
Z4 represents CR19R20 or C=CR17R18;
each R15 and R16 independently of one another represent hydrogen, halogen, CN, OH, d-d alkyl or CrC4 haloalkyi;
each R17 and R18 independently of one another represent hydrogen, halogen, methyl or halomethyl;
each R19 and R20 independently of one another represent hydrogen, halogen, CN, OH, d-d alkyl, d-C4 haloalkyi or phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
or R19 and R20 together with the carbon atom to which they are attached may form a
C3-C6 cycloalkyi group or a C3-C6 halocycloalkyl group;
wherein at least two of Z3, Z4 and Z5 are methylene;
Y1, Y2, and Y3 independently of one another represent hydrogen, halogen, OH, CN, d-d alkyl, CrC4 alkoxy, C3-C6 alkenyloxy, C3-C6 cycloalkyi, N(R10)2, phenyl or C02R8, wherein the alkyl, alkoxy, alkenyloxy, cycloalkyi and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, Crd alkyl, d-C4-haloalkyl, Crd alkoxy and d-C4 haloalkoxy;
each R8 independently or one another represents hydrogen, Crd alkyl or Crd haloalkyi;
each R10 independently of one another represents hydrogen or Crd alkyl; wherein when two radicals R are attached to the same nitrogen atom, these radicals can be identical or different;
and wherein when two radicals R11 are attached to the same nitrogen atom, these two radicals together with the nitrogen atom to which they are attached may form a cycle B- 1, B-2, B-3, B-4 or B-5, wherein the cycle formed is optionally substituted by one or more groups independently selected from halogen, methyl and halomethyl.
In one group of compounds, R1 represents Ci-C4 alkyl, C2-C4 alkenyl, phenyl or pyridyl, wherein the alkyl, alkenyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, Ci-C4 alkoxy and Ci-C4 haloalkoxy.
In one group of compounds R3 represents pyridyl, optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, Ci-C4 alkyl, Ci-C4 haloalkyl, d-C4 alkoxy, CrC4 haloalkoxy, C3-C6 cycloalkyl and a 5- or 6-membered
heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms.
The heterocycle is preferably one as defined herein, preferably morpholinyl, pyrrolidinyl, piperdinyl, piperazinyl, pyridyl, pyrrolyl, imidazolyl or triazolyl, e.g. 1,2,4 triazolyl, more preferably morpholinyl, pyrollidinyl, pyridyl or imidazolyl.
In another group of compounds A1 is Ala and R3 represents pyridin-2-yl, optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, CrC4-alkyl, CrC4-haloalkyl, d-C4-alkoxy, CrC4-haloalkoxy, C3-C6 cycloalkyl and a 5 or 6- membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms. The heterocycle is preferably one as defined herein, preferably morpholinyl, pyrrolidinyl, piperdinyl, piperazinyl, pyridyl, pyrrolyl, imidazolyl or triazolyl, e.g. 1,2,4 triazolyl, more preferably morpholinyl, pyrollidinyl, pyridyl or imidazolyl.
In another group of compounds A1 and R3 represent identical substituents.
In another group of compounds:
X represents X-3;
Z3 and Z5 represent methylene;
Z4 represents CR19R20 or C=CR17R18;
each R17 and R18 independently of one another represent hydrogen, halogen, methyl or halomethyl;.
each R19 and R20 independently of one another represent hydrogen, halogen, CN, OH,
CrC4 alkyl, CrC4 haloalkyl or phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
or R19 and R20 together with the carbon atom to which they are attached may form a C3-C5 cycloalkyl group optionally substituted by halogen.
In one group of compounds, Y1 and Y3, Y2 and Y3, R5 and R6, R6 and R4, or R4 and R7 together with the fragment of the pyridyl ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from O, S, N and N(R5), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, and wherein the ring formed by Y1 and Y3, Y2 and Y3, R5 and R6, R6 and R4, or R4 and R7 is optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, d-C4 alkyl, d-C4 haloalkyl, Q-C4 alkoxy and CrC4 haloalkoxy.
Preferably in this group of compounds, Y1 and Y3, Y2 and Y3, R5 and R6, R6 and R4, or R4 and R7, together with the fragment of the ring to which they are attached may form a fully or partially unsaturated 6-membered carbocyclic ring optionally substituted by one or more groups independently selected from halogen, methyl and halomethyl.
In another group of compounds, R5 and R6, R6 and R4, or R4 and R7 together with the fragment of the ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from O, S, N and N(R5), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, and wherein the ring formed by R5 and R6, R6 and R4, or R4 and R7 is optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, Q-G, alkyl, CrC haloalkyl, Q-G, alkoxy and Q-G, haloalkoxy.
In this group of compounds, R5 and R6, R6 and R4, or R4 and R7, together with the fragment of the ring to which they are attached may preferably form a fully or partially unsaturated 6-membered carbocyclic ring optionally substituted by one or more groups independently selected from halogen, methyl and halomethyl.
In any group of compounds wherein R5 and R6, R6 and R4, or R4 and R7, together with the fragment of the ring to which they are attached may form ring, preferably this ring will only be formed by R5 and R6 together with the fragment of the ring to which they are attached.
In another group of compounds: R1 represents hydrogen, C1-C4 alkyl, C1-C4 haloalkyl and phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
R2 represents hydrogen, d-d alkyl, C3-C6 alkenyl or C3-C6 alkynyl, wherein the alkyl, alkenyl, or alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, d-d alkoxy and d-d haloalkoxy;
D1 represents C-Y1;
D2 represents C-Y2;
A represents group A-l, A-2, or A-3;
A1 represents the cycle Ala, Al , or Alc;
R3 represents hydrogen, CN, d-d alkyl, C3-C6 cycloalkyi, C2-C4 alkenyl, C2-C4 alkynyl, (CrC4alkoxy)carbonyl(d-C4 alkyl), phenyl or pyridyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, NH-CrC8 alkyl, N(CrC8 alkyl)2, N02, OH, CrC4 alkyl, CrC4 haloalkyl, C3-C6 cycloalkyi, pyridyl or pyrroline;
R4 represents hydrogen, halogen, CN, Ci-C6 alkyl, C3-C6 cycloalkyi, C2-C6 alkenyl, C2- C6 alkynyl, phenyl, OH, CrC4 alkoxy, NH2, NH(CrC4 alkyl), N(CrC4 alkyl)2, CO(CrC4 alkyl), wherein the alkyl, cycloalkyi, alkenyl, alkynyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
R5 represents hydrogen, halogen, CN, Ci-C8 alkyl, C3-C6 cycloalkyi, C2-C8 alkenyl, C2- C8 alkynyl, phenyl, pyridyl, CO(CrC4 alkyl), OH, CrC4 alkoxy, NH2, NH(CrC4 alkyl), N(CrC4 alkyl)2 or C02(d-C4 alkyl), wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, OR8, Ci-d alkyl, CrC4 haloalkyl;
R6 represents hydrogen, halogen, CN, Ci-d alkyl, C3-C6 cycloalkyi, C2-C6 alkenyl, C2- C6 alkynyl, phenyl, Crd alkoxy or benzyloxy, wherein the alkyl, cycloalkyi, alkenyl, alkynyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
or R5 and R6 together with the fragment of the ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a partially or fully unsaturated 5- to 7-membered heterocyclic ring containing one heteroatom independently selected from O, S, N NH and N(d-C4 alkyl), wherein the ring formed is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy; R7 represents hydrogen, halogen, CN, Q-C4 alkyi, C3-C6 cycloalkyi, C2-C4 alkenyl, C2- C4 alkynyl, OH, CrC4 alkoxy, NH2, NH(CrC4 alkyi), N(CrC4 alkyl)2, C02(CrC4 alkyi) and C02(Ci-C4 alkyi), wherein the alkyi, cycloalkyi, alkenyl and alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
G1 and G2 independently of one another represent -C(R12R13)-;
G3 represents -C(R12R13)-, O, N(R14) or S;
each R12 and R13 independently of one another represent hydrogen, halogen, Ci-C4 alkyi, Ci-C4 haloalkyl, Ci-C4 alkoxy or Ci-C4 haloalkoxy;
R14 represents hydrogen, OH, Ci-C4 alkyi, Ci-C4 alkoxy, C3-C6 cycloalkyi, Ci-C8 alkylcarbonyl or Ci-C8 haloalkylcarbonyl;
p represents 1 or 2;
X represents X-3;
Z3 and Z5 independently of one another represent CR15R16 or C=CR17R18;
Z4 represent CR19R20;
each R15 and R16 independently of one another represent hydrogen, halogen, d-C4 alkyi or d-C4 haloalkyl;
each R17 and R18 independently of one another represent hydrogen, halogen, methyl or halomethyl;
each R19, R20 independently of one another represent hydrogen, halogen, CN, OH,
Ci-G, alkyi or Q-G, haloalkyl;
or R19 and R20 together with the carbon atom to which they are attached may form a C3-C6 cycloalkyi group or a C3-C6 halocycloalkyl group;
Y1 and Y2 each represent H;
Y3 represents hydrogen, halogen, CN, Ci-C4 alkyi, C3-C6 cycloalkyi, C2-C6 alkenyl, C2-C6 alkynyl or d-C4 alkoxy wherein the alkyi, cycloalkyi, alkenyl and alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, Ci-C, alkyi and Q-C, haloalkyl;
each R8 independently of one another represents hydrogen, d-C8 alkyi, C3-C8 cycloalkyi, C3-C8 alkenyl, C3-C8 alkynyl, phenyl, benzyl or pyridyl, wherein the alkyi, cycloalkyi, alkenyl, alkynyl, phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, d-C4 alkyi, d-C4- haloalkyl, d-C4 alkoxy, CrC4 haloalkoxy and CrC4-alkoxy-CrC4-alkyl.
In a further group of compounds: R1 represents hydrogen, C1-C4 alkyl, C1-C4 haloalkyl and phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
R2 represents hydrogen, d-d alkyl, C3-C6 alkenyl or C3-C6 alkynyl, wherein the alkyl, alkenyl, or alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
D1 represents C-Y1;
D2 represents C-Y2;
A represents group A-l, A-2, or A-3;
A1 represents the cycle Ala, Al , or Alc;
R3 represents hydrogen, CN, d-d alkyl, C2-d alkenyl, C2-d alkynyl or phenyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl and phenyl pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, NH-Crd alkyl, N(Crd alkyl)2, OH, Crd alkyl, Crd haloalkyl, C3-C6 cycloalkyi, pyridyl or pyrroline;
R4 represents hydrogen, halogen, CN, Ci-C6 alkyl, C3-C6 cycloalkyi, C2-C4 alkenyl, C2-
C4 alkynyl, phenyl, Crd alkoxy, or CO(CrC4 alkyl), wherein the alkyl, cycloalkyi, alkenyl, alkynyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
R5 represents hydrogen, halogen, CN, Ci-C8 alkyl, C3-C6 cycloalkyi, C2-C8 alkenyl, C2- C8 alkynyl, phenyl, pyridyl, CO(CrC4 alkyl), OH, Crd alkoxy, NH2, NH(CrC4 alkyl), N(CrC4 alkyl)2 or C02(d-C4 alkyl), wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, OR8, d-d alkyl, CrC4 haloalkyl;
R6 represents hydrogen, halogen, CN, d-C4 alkyl, Crd alkoxy or benzyloxy, wherein the alkyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
or R5 and R6 together with the fragment of the ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a partially or fully unsaturated 5- to 7-membered heterocyclic ring containing one heteroatom independently selected from O or S, wherein the ring formed is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
R7 represents hydrogen, halogen, CN, d-C4 alkyl, C3-C6 cycloalkyi, C2-C4 alkenyl, C2- d alkynyl, OH, CrC4 alkoxy, NH2, NH(CrC4 alkyl), N(CrC4 alkyl)2, C02(CrC4 alkyl) and C02(d-C4 alkyl), wherein the alkyl, cycloalkyi, alkenyl and alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
G1 represents -CH2-;
G2 represents -C(R12R13)-;
G3 represents -C(R12R13)-, O, N(R14) or S;
each R12 and R13 independently of one another represent hydrogen or C1-C4 alkyl;
R14 represents hydrogen or d-d alkyl;
p represents 1 or 2;
X represents X-3;
Z3 and Z5 independently of one another represent CR15R16 or C=CR17R18;
Z4 represent CR19R20;
each R15 and R16 independently of one another represent hydrogen, halogen, Crd alkyl or Crd haloalkyl;
each R17 and R18 independently of one another represent hydrogen, halogen, methyl or halomethyl;
each R19, R20 independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl or CHd haloalkyl;
or R19 and R20 together with the carbon atom to which they are attached may form a C3-C6 cycloalkyi group or a C3-C6 halocycloalkyl group;
wherein the grouping X-3 contains at most one ring which contains either only one of the radicals Z3 to Z5 or two radicals Z3 to Z5 or three radicals Z3 to Z5 as ring members;
Y1 and Y2 each represent H;
Y3 represents hydrogen, halogen, CN, Crd alkyl, C2-C6 alkenyl, C2-C6 alkynyl or Crd alkoxy wherein the alkyl, cycloalkyi, alkenyl and alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, Crd alkyl and Crd haloalkyl;
each R8 independently of one another represents hydrogen, d-C6 alkyl, C3-C6 alkenyl, C3-d alkynyl, phenyl or benzyl.
The invention also rovides compounds of formula I-i
(l-i)
Figure imgf000031_0001
wherein A1, and preferred defintiions thereof, are as defined for compounds of formula I.
The invention also rovides compounds of formula I-ii
Figure imgf000032_0001
wherein R4, R5 and R6, and preferred defintiions thereof, are as defined for pounds of formula I.
The invention also rovides compounds of formula I-iii
Figure imgf000032_0002
wherein R4 and R5, and preferred defintiions thereof, are as defined for compounds of formula I. Intermediates that can be used to prepare compounds of formula (I) also form part of the present invention.Accordingly, in a further aspect, the invention provides a compound of formula (II)
Figure imgf000032_0003
wherein D1, D2, X, Y1, Y2, Y3, R1 and R2 are as defined herein for compounds of formula (I); or a salt or N-oxide thereof. The preferred definitions of X, Y1, Y2, Y3, R1 and R2 defined in respect of compounds of formula (I) also apply to compounds of formula (II).
In a further aspect, the invention provides a compound of formula (III)
Figure imgf000033_0001
wherein T1 and T2 independently of one another represent Ci-C8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-Ci-C6-alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C6 alkyl;
D1, D2, A, X, Y1, Y2, Y3 and R1 are as defined herein for compounds of formula (I); or a salt or N-oxide thereof. The preferred definitions of A, R1, X, Y1, Y2, Y3 and R2 defined in respect of compounds of formula (I) also apply to compounds of formula (III).
In a further aspect, the invention provides a compound of formula (IV)
Figure imgf000033_0002
wherein X' represents X'-l, X'-2 or X'-3
#— z— # #—∑—∑—# #—z—z—z—#
X'-1 X'-2 X'-3
wherein D1, D2, A, Z3, Z6, Z7, Z10, Z11, Z12, Y1, Y2, Y3, R1 and R2 are as defined herein for compounds of formula (I); or a salt or N-oxide thereof. The preferred definitions of A, Z3, Z6, Z7, Z10, Z11, Z12, Y1, Y2, Y3, R1 and R2 defined in respect of compounds of formula (I) also apply to compounds of formula (VI).
In a further aspect, the invention provides a compound of formula (V)
Figure imgf000033_0003
(V)
wherein X' represents X'-l, X'-2 or X'-3 #—∑—# #—∑—∑—# #—∑—∑—∑—#
X'-1 X'-2 Χ'-3
Τ1 and Τ2 independently of one another represent CrC8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC6-alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C6 alkyl;
D1, D2, A, Z3, Z6, Z7, Z10, Z11, Z12, Y1, Y2, Y3 and R1 are as defined herein for a compound of formula (I); or a salt or N-oxide thereof. The preferred definitions of A, Z3, Z6, Z7, Z10, Z11, Z12, Y1, Y2, Y3 and R1 defined in respect of compounds of formula (I) also apply to compounds of formula (V).
In a further aspect, the invention provides a compound of formula (VI)
Figure imgf000034_0001
wherein X' represents X'-l, X'-2 or X'-3
#—∑—# #—∑—∑—# #—∑—∑—∑—#
X'-1 X'-2 X'-3
R23 and R24 independently of one another represent hydrogen, halogen, CN, Q-C4 alkyl, Ci-C4 haloalkyl or phenyl, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-C4 alkyl, CrC4 haloalkyl, Q-C4 alkoxy and CrC4 haloalkoxy;
D1, D2, A, Z3, Z6, Z7, Z10, Z11, Z12, Y1, Y2, Y3, R1 and R2 are as defined herein for a compound of formula (I); or a salt or N-oxide thereof. The preferred definitions of A, Z3, Z6, Z7, Z10, Z11, Z12, Y1, Y2, Y3, R1 and R2 defined in respect of compounds of formula (I) also apply to compounds of formula (VI).
In a further aspect, the invention provides a compound of formula (VII)
Figure imgf000034_0002
wherein X' represents X'-l, X'-2 or X'-3
#— z— # #—∑—∑—# #—z—z—z—#
X'-1 X'-2 X'-3
R23 and R24 independently of one another represent hydrogen, halogen, CN, Ci-C4 alkyl, Q- haloalkyl or phenyl, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-C4 alkyl, CrC4 haloalkyl, d-C4 alkoxy and CrC4 haloalkoxy;
T1 and T2 independently of one another represent CrC8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC6-alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C6 alkyl;
D1, D2, A, Z3, Z6, Z7, Z10, Z11, Z12, Y1, Y2, Y3 and R1 are as defined herein for compounds of formula (I); or a salt or N-oxide thereof. The preferred definitions of A, Z3, Z6, Z7, Z10, Z11, Z12, Y1, Y2, Y3 and R1 defined in respect of compounds of formula (I) also apply to compounds of formula (VII).
In a further aspect, the invention provides a compound of formula (VIII)
Figure imgf000035_0001
wherein X' represents X'-l, X'-2 or X'-3
#— z— # #—∑—∑—# #—z—z—z—#
X'-1 X'-2 X'-3
D1, D2, Z3, Z6, Z7, Z10, Z11, Z12, Y1, Y2, Y3, R1 and R2 are as defined herein for a compound of formula (I); or a salt or N-oxide thereof. The preferred definitions of Z3, Z6, Z7, Z10, Z11, Z12, Y1, Y2, Y3, R1 and R2 defined in respect of compounds of formula (I) also apply to compounds of formula (VIII).
In a further aspect, the invention provides a compound of formula (IX)
Figure imgf000036_0001
wherein X' represents X'-l, X'-2 or X'-3
#— z— # #—∑—∑—# #—z—z—z—#
X'-1 X'-2 X'-3
D1, D2, Z3, Z6, Z7, Z10, Z11, Z12, Y1, Y2, Y3, R1 and R2 are as defined herein for a compound of formula (I); or a salt or N-oxide thereof. The preferred definitions of Z3, Z6, Z7, Z10, Z11, Z12, Y1, Y2, Y3, R1 and R2 defined in respect of compounds of formula (I) also apply to compounds of formula (IX).
In a further aspect, the invention provides a compound of formula (X)
Figure imgf000036_0002
wherein X' represents X'-l, X'-2 or X'-3
#— z— # #—∑—∑—# #—z—z—z—#
X'-1 X'-2 X'-3
D1, D2, Z3, Z6, Z7, Z10, Z11, Z12, Y1, Y2, Y3, R1 and R2 are as defined herein for a compound of formula (I); or a salt or N-oxide thereof. The preferred definitions of Z3, Z6, Z7, Z10, Z11, Z12, Y1, Y2, Y3, R1 and R2 defined in respect of compounds of formula (I) also apply to compounds of formula (X).
In a further aspect, the invention provides a compound of formula (XI)
Figure imgf000036_0003
(XI) wherein R is a halogen or a sulfonic acid ester group, e.g. bromine, iodine, mesylate, triflate, phenylsulfonic acid ester or nonafluorobutylsulfonic acid ester, wherein the phenylsulfonic acid ester is optionally substituted by one or more groups independently selected from halogen, N02, CN, d-d alkyl, d-d haloalkyl, Ci-d alkoxy and d-d haloalkoxy, for example tosylate or nitro-phenylsulfonic acid ester;
T1 and T2 independently of one another represent d-C8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-Ci-C6-alkylidene-0) whereby the alkylidene fragment, wherein the alkylidene fragment is optionally substituted by one to four d-C6 alkyl;
X' represents X'-l, X'-2 or X'-3
#— z— # #—∑—∑—# #—z—z—z—#
X'-1 X'-2 X'-3
D1, D2, Z3, Z6, Z7, Z10, Z11, Z12, Y1, Y2, Y3 and R1 are as defined herein for a compound of formula (I); or a salt or N-oxide thereof. The preferred definitions of Z3, Z6, Z7, Z10, Z11, Z12, Y1, Y2, Y3 and R2 defined in respect of compounds of formula (I) also apply to compounds of formula (XI).
In a further aspect, the invention provides a compound of formula (XII)
Figure imgf000037_0001
wherein X' represents X'-l, X'-2 or X'-3
#— z— # #—∑—∑—# #—z—z—z—#
X'-1 X'-2 X'-3
A, Z3, Z6, Z7, Z10, Z11 and Z12 are as defined herein for a compound of formula (I); or a salt or N-oxide thereof. The preferred definitions of A, Z3, Z6, Z7, Z10, Z11 and Z12 defined in respect of compounds of formula (I) also apply to compounds of formula (XII).
In a further aspect, the invention provides a compound of formula (XIII)
Figure imgf000037_0002
(XIII)
wherein X' represents X'-l, X'-2 or X'-3 #—∑—# #—∑—∑—# #—∑—∑—∑—#
X'-1 X'-2 Χ'-3
Τ1 and Τ2 independently of one another represent CrC8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC6-alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C6 alkyl;
D1, D2, Z3, Z6, Z7, Z10, Z11, Z12, Y1, Y2, Y3 and R1 are as defined herein for a compound of formula (I); or a salt or N-oxide thereof. The preferred definitions of Z3, Z6, Z7, Z10, Z11, Z12, Y1, Y2, Y3 and R1 defined in respect of compounds of formula (I) also apply to compounds of formula (XII).
In a further aspect, the invention provides a compound of formula (XV)
Figure imgf000038_0001
(XV)
wherein R is a halogen or a sulfonic acid ester group, e.g. bromine, iodine, mesylate, tosylate, triflate, phenylsulfonic acid ester, nitro-phenylsulfonic acid ester, or nonafluorobutylsulfonic acid ester, wherein the phenylsulfonic acid ester is optionally substituted by one or more groups independently selected from halogen, N02, CN, d-d alkyl, d-d haloalkyl, d-d alkoxy and d-d haloalkoxy, for example tosylate or nitro- phenylsulfonic acid ester;
X' represents X'-l, X'-2 or X'-3
#—∑—# #—∑—∑—# #—∑—∑—∑—#
X'-1 X'-2 X'-3
R23 and R24 independently of one another represent hydrogen, halogen, CN, Ci-d alkyl, Ci-d haloalkyl or phenyl, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, Crd alkyl, d-d haloalkyl, Crd alkoxy and Crd haloalkoxy;
T1 and T2 independently of one another represent d-C8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-Ci-C6-alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C6 alkyl; D1, D2, Z3, Z6, Z7, Z10, Z11, Z12, Y1, Y2, Y3 and R1 are as defined herein for a compound of formula (I); or a salt or N-oxide thereof. The preferred definitions of Z3, Z6, Z7, Z10, Z11, Z12, Y1, Y2, Y3 and R2 defined in respect of compounds of formula (I) also apply to compounds of formula (XV).
Preferably the compound of formula (XV) is a compound of formula (XVII)
Figure imgf000039_0001
(XVII)
wherein R is a halogen or a sulfonic acid ester group, e.g. bromine, iodine, mesylate, tosylate, triflate, phenylsulfonic acid ester, nitro-phenylsulfonic acid ester, or nonafluorobutylsulfonic acid ester, wherein the phenylsulfonic acid ester is optionally substituted by one or more groups independently selected from halogen, N02, CN, d-C4 alkyl, d-C4 haloalkyl, d-C4 alkoxy and CrC4 haloalkoxy, for example tosylate or nitro- phenylsulfonic acid ester;
R23 and R24 independently of one another represent hydrogen, halogen, CN, Ci-C4 alkyl, Ci-C4 haloalkyl or phenyl, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-C4 alkyl, d-C4 haloalkyl, d-C4 alkoxy and d-C4 haloalkyoxy;
T1 and T2 independently of one another represent d-C8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC6-alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C6 alky;
D1, D2, Y1, Y2, Y3 and R1 are as defined herein for a compound of formula (I); or a salt or N-oxide thereof. The preferred definitions of Y1, Y2, Y3 and R1 defined in respect of compounds of formula (I) also apply to compounds of formula (XVII).
In a further aspect, the invention provides a compound of formula (XVI)
Figure imgf000039_0002
(XVI) wherin R represents hydrogen, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl or phenyl, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-d alkyl, d-d haloalkyl, Crd alkoxy and d-d haloalkoxy;
T1 and T2 independently of one another represent d-C8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-Ci-C6-alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C6 alkyl;
D1, D2, Y1, Y2, Y3 and R1 are as defined herein for compounds of formula (I); or a salt or N-oxide thereof. The preferred definitions of Y1, Y2, Y3 and R1 defined in respect of compounds of formula (I) also apply to compounds of formula (XVI).
In a further aspect, the invention provides a compound of formula (XVIII)
Figure imgf000040_0001
(XVIII)
wherein R23 and R24 independently of one another represent hydrogen, halogen, CN, C1-C4 alkyl, Ci- haloalkyl or phenyl, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, Crd alkyl, d-d haloalkyl, Crd alkoxy and Crd haloalkoxy;
T1 and T2 independently of one another represent d-C8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC6-alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C6 alkyl;
D1, D2, Y1, Y2, Y3 and R1 are as defined for a compound of formula (I); or a salt or N-oxide thereof. The preferred definitions of Y1, Y2, Y3 and R1 defined in respect of compounds of formula (I) also apply to compounds of formula (XVIII).
In a further aspect, the invention provides a compound of formula (XIX)
Figure imgf000041_0001
wherein R represents CrC4 alkyl;
R23 and R24 independently of one another represent hydrogen, halogen, CN, Q-C4 alkyl, Ci-C4 haloalkyl or phenyl, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-C4 alkyl, CrC4 haloalkyl, d-C4 alkoxy and CrC4 haloalkoxy;
T1 and T2 independently of one another represent CrC8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC6-alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C6 alkyl;
D1, D2, Y1, Y2, Y3 and R1 are as defined for a compound of formula (I); or a salt or N-oxide thereof. The preferred definitions of Y1, Y2, Y3 and R1 defined in respect of compounds of formula (I) also apply to compounds of formula (XIX).
The compounds of formula (I) may exist as different geometric or optical isomers or in different tautomeric forms. These may be separated and isolated by well-known (usually chromatographic) techniques, and all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms, such as deuterated compounds, are part of the present invention. In particular, the carbon-nitrogen double bonds of the compound of formula (I) allow the four cis/trans isomers exemplified using compounds where A is A-l below:
Figure imgf000042_0001
The present invention includes each of these isomers. The invention may provide a compound of formula (I) as just one of these isomers or as a mixture of one or more isomers in any ratio. Likewise, the invention also includes the corresponding isomers of the intermediates described herein, in particular compounds (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), (XII), (XIII), (XIV), (XV), (XVI), (XVII), (XVIII) and (XIX). In addition, where a reaction scheme depicts synthesis of one geometric isomer, the scheme also includes synthesis of the other geometric isomers where possible. For example reaction scheme A shown below encompasses reaction schemes B, C and D:
Figure imgf000043_0001
The compounds in tables 1 to 15 illustrate compounds of formula (I).
5 Table X
Table X represents Table 1 (when X is 1), Table 2 (when X is 2), Table 3 (when X is 3), Table 4 (when X is 4), Table 5 (when X is 5), Table 6 (when X is 6), Table 7 (when X is 7), Table 8 (when X is 8), Table 9 (when X is 9), Table 10 (when X is 10), Table 11 (when X is 11), Table 12 (when X is 12), Table 13 (when X is 13), Table 14 (when X is 14) and Table 10 15 (when X is 15). In all compounds of Table 1-15, A is A-l, wherein A1 is Ala
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
cyclopropylpyridin-2-yl
Figure imgf000057_0001
methylpyridin-2-yl
Figure imgf000058_0001
methoxypyridin-2-yl
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
x.563 Pyridin-2-yl CH2CH3 H H H
Table 1 : This table discloses compounds 1.001 to 1.563 of the formula (I-I)
Figure imgf000062_0002
wherein Ala, R3, Y1, Y2 and Y3 have the specific meanings given in Table X. Table 2: This table discloses compounds 2.001 to 2.563 of the formula (I-II)
Figure imgf000063_0001
wherein Ala, R3, Y1, Y2 and Y3 have the specific meanings given in Table X. Table 3: This table discloses compounds 3.001 to 3.563 of the formula (I-III)
Figure imgf000063_0002
wherein Ala, R3, Y1, Y2 and Y3 have the specific meanings given in Table X.
Table 4: This table discloses compounds 4.001 to 4.563 of the formula (I-IV)
Figure imgf000063_0003
wherein Ala, R3, Y1, Y2 and YJ have the specific meanings given in Table X. Table 5: This table discloses compounds 5.001 to 5.563 of the formula (I-V)
Figure imgf000064_0001
wherein Ala, R3, Y1, Y2 and YJ have the specific meanings given in Table X. Table 6: This table discloses compounds 6.001 to 6.563 of the formula (I-VI)
Figure imgf000064_0002
wherein Ala, R3, Y1, Y2 and Y3 have the specific meanings given in Table X.
Table 7: This table discloses compounds 7.001 to 7.563 of the formula (I-VII)
Figure imgf000064_0003
wherein Ala, R3, Y1, Y2 and YJ have the specific meanings given in Table X.
Table 8: This table discloses compounds 8.001 to 8.563 of the formula (I-VIII)
Figure imgf000064_0004
wherein Ala, R3, Y1, Y2 and Y3 have the specific meanings given in Table X.
Table 9: This table discloses compounds 9.001 to 9.563 of the formula (I-IX)
Figure imgf000065_0001
wherein Ala, R3, Y1, Y2 and Y3 have the specific meanings given in Table X. Table 10: This table discloses compounds 10.001 to 10.563 of the formula (I-X)
Figure imgf000065_0002
wherein Ala, R3, Y1, Y2 and Y3 have the specific meanings given in Table X.
Table 11: This table discloses compounds 11.001 to 11.563 of the formula (I-XI)
Figure imgf000065_0003
wherein Ala, R3, Y1, Y2 and Y3 have the specific meanings given in Table X. Table 12: This table discloses compounds 12.001 to 12.563 of the formula (I-XII)
Figure imgf000066_0001
wherein Ala, R3, Y1, Y2 and Y3 have the specific meanings given in Table X.
Table 13: This table discloses compounds 13.001 to 13.563 of the formula (I-XIII)
Figure imgf000066_0002
wherein Ala, R3, Y1, Y2 and Y3 have the specific meanings given in Table X.
Table 14: This table discloses compounds 14.001 to 14.563 of the formula (I-XIV)
Figure imgf000066_0003
wherein Ala, R3, Y1, Y2 and YJ have the specific meanings given in Table X.
Table 15: This table discloses compounds 15.001 to 15.563 of the formula (I-XV)
Figure imgf000066_0004
wherein Ala, R3, Y1, Y2 and Y3 have the specific meanings given in Table X. Table Y
Table Y represents Table 16 (when Y is 16), Table 17 (when Y is 17), Table 18 (when Y is 18), Table 19 (when Y is 19), Table 20 (when Y is 20), Table 21 (when Y is 21), Table 22 (when Y is 22), Table 23 (when Y is 23), Table 24 (when Y is 24), Table 25 (when Y is 25), Table 26 (when Y is 26), Table 27 (when Y is 27), Table 28 (when Y is 28), Table 29 (when Y is 29), Table 30 (when Y is 30), and Table 31 (when Y is 31).
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Table 16: This table discloses compounds 16.001 to 16.479 of the formula (I-XVI)
Figure imgf000083_0001
wherein Y1, Y2, Y3, R4, R5 and Rs have the specific meanings given in Table Y.
Table 17: This table discloses compounds 17.001 to 17.479 of the formula (I-XVII)
Figure imgf000083_0002
wherein Y1, Y2, Y3, R4, R5 and R have the specific meanings given in Table Y.
Table 18: This table discloses compounds 18.001 to 18.479 of the formula (I-XVIII)
(I-XVIII)
Figure imgf000083_0003
wherein Y1, Y2, Y3, R4, R5 and R have the specific meanings given in Table Y. Table 19: This table discloses compounds 19.001 to 19.479 of the formula (I-XIX)
Figure imgf000084_0001
wherein Y1, Y2, Y3, R4, R5 and Rs have the specific meanings given in Table Y. Table 20: This table discloses compounds 20.001 to 20.479 of the formula (I-XX)
Figure imgf000084_0002
wherein Y1, Y2, Y3, R4, R5 and R have the specific meanings given in Table Y.
Table 21: This table discloses compounds 21.001 to 21.479 of the formula (I-XXI)
Figure imgf000084_0003
wherein Y1, Y2, Y3, R4, R5 and R have the specific meanings given in Table Y.
Table 22: This table discloses compounds 22.001 to 22.479 of the formula (I-XXII)
Figure imgf000085_0001
wherein Y1, Y2, Y3, R4, R5 and R have the specific meanings given in Table Y.
Table 23: This table discloses compounds 23.001 to 23.479 of the formula (I-XXIII)
(I-XXIII)
Figure imgf000085_0002
wherein Y1, Y2, Y3, R4, R5 and Rs have the specific meanings given in Table Y.
Table 24: This table discloses compounds 24.001 to 24.479 of the formula (I-XXIV)
Figure imgf000085_0003
wherein Y1, Y2, Y3, R4, R5 and Rs have the specific meanings given in Table Y.
Table 25: This table discloses compounds 25.001 to 25.479 of the formula (I-XXV)
Figure imgf000086_0001
wherein Y , Y , Y , Y , Y and Y have the specific meanings given in Table Y.
Table 26: This table discloses compounds 26.001 to 26.4793 of the formula (I-XXVI)
Figure imgf000086_0002
wherein Y1, Y2, Y3, R4, R5 and Rb have the specific meanings given in Table Y.
Table 27: This table discloses compounds 27.001 to 27.479 of the formula (I-XXVII)
(I-XXVII)
Figure imgf000086_0003
wherein Y1, Y2, Y3, R4, R5 and Rb have the specific meanings given in Table Y.
Table 28: This table discloses compounds 28.001 to 28.479 of the formula (I-XXVIII) (l-XXVIII)
Figure imgf000087_0001
wherein Y1, Y2, Y3, R4, R5 and R have the specific meanings given in Table Y.
Table 29: This table discloses compounds 29.001 to 29.479 of the formula (I-XXIX)
Figure imgf000087_0002
wherein Y , Y , Y , R , R and R have the specific meanings given in Table Y.
Table 30: This table discloses compounds 30.001 to 30.479 of the formula (I-XXX)
Figure imgf000087_0003
wherein Y1, Y2, Y3, R4, R5 and Rs have the specific meanings given in Table Y.
Table 31: This table discloses compounds 31.001 to 31.479 of the formula (I-XXXI)
Figure imgf000088_0001
wherein Y1, Y2, Y3, R4, R5 and R6 have the specific meanings given in Table Y. Table Z
Table Z represents Table 32 (when Z is 32), Table 33 (when Z is 33), Table 34 (when Z is 34)
Figure imgf000088_0002
Figure imgf000089_0001
Table 32: This table discloses compounds 32.001 to 32.043 of the formula (I-XXXII)
(l-XXXII)
Figure imgf000089_0002
wherein X represents -CH2-CH2-CH2- and A, Y3, G^G^G3, R4, R5, R6 and R7 have the specific meanings given in Table Z.
Table 33: This table discloses compounds 33.001 to 33.043 of the formula (I-XXXIII)
(l-XXXIII)
Figure imgf000090_0001
wherein X represents -CH2-CH2-CH2- and A, Y3, G^G^G3, R4, R5, R6 and R7 have the specific meanings given in Table Z.
Table 34: This table discloses compounds 34.001 to 34.043 of the formula (I-XXXIV)
(l-XXXIV)
Figure imgf000090_0002
wherein X represents -CH2-CH2-CH2- and A, Y3, G^G^G3, R4, R5, R6and R7 have the specific meanings given in Table Z.
The compounds in Tables 1 to 34 include all isomers, tautomers and mixtures thereof, including the cis/trans isomers shown above.
The compounds of the invention may be made by a variety of methods, illustrated in schemes 1-12. The compounds depicted in the schemes also indicate any isomers and tautomers, in particular the geometric isomers arising from the oxime and oxime ether moieties. Scheme 1:
Figure imgf000091_0001
1) Compounds of formula (I) may be prepared by reacting a compound of formula (II) with a compound of formula (XX), wherein R27 represents group A-6, A-7, A-8, A-9 or A- 5 10:
Figure imgf000091_0002
A-9 A-10
T1 and T2 are Q-C8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC6-alkylidene-0) whereby the alkylidene fragment may optionally be mono- to tetra-substituted by CrC6 alkyl 10 and D1, D2, R3, R5, R6 and R7 are as defined herein for compounds of formula (I), as seen in scheme 1.
A general description of condensation reactions is given below, and typical reaction conditions for this type of reaction may be found in Journal of Organic Chemistry, 52(22), 4978-84; 1987; Chemical & Pharmaceutical Bulletin, 51(2), 138-151; 2003; Organic Letters,
15 10(2), 285-288; 2008; Journal of the American Chemical Society, 130(12), 4196-4201; 2008;
Chemistry & Biology, 9(1), 113-129; 2002; Organic Preparations and Procedures
International, 32(2), 153-159; 2000; Scientia Pharmaceutica, 66(1), 9-21; 1998, Journal of Medicinal Chemistry, 49(17), 5177-5186; 2006, Journal of Agricultural and Food Chemistry, 38(3), 839-44; 1990; Tetrahedron: Asymmetry, 8(2), 253-263; 1997; Journal of Medicinal
20 Chemistry, 44(21), 3339-3342; 2001; Bioorganic & Medicinal Chemistry Letters, 12(3), 341- 344; 2002; US 2007032470; WO 07/058504; Journal of Organic Chemistry, 73(5), 2007- 2010; 2008; Bioorganic & Medicinal Chemistry Letters, 19(10), 2683-2687; 2009; and Bioorganic & Medicinal Chemistry Letters, 19(10), 2654-2660; 2009.
Scheme 2
Figure imgf000092_0001
2) Alternatively, as seen in scheme 2, compounds of formula (I) may be prepared by reacting a compound of formula (III), wherein D1, D2, A, X, and Y3 and R1 are as defined herein for compounds of formula (I) and T1 and T2 are CrC8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC6-alkylidene-0) whereby the alkylidene fragment may optionally be mono- to tetra-substituted by Q-C6 alkyl, and a compound of formula (XXI), wherein R2 is as defined herein for compounds of formula (I) under conditions described in procedure 1.
3) Alternatively, as seen in scheme 2, compounds of formula (I) may be prepared by reacting a compound of formula (la), that is a compound of formula (I) wherein R2 is hydrogen, and a compound of formula (XXII), wherein R2 is as defined herein for compounds of formula (I) and R25 is a halogen, in particular chlorine, bromine or iodine, or a sulfonic acid ester group, such as mesylate, tosylate, triflate, phenylsulfonic acid ester, nitro- phenylsulfonic acid ester, or nonafluorobutylsulfonic acid ester.
Typical reaction conditions for alkylation reactions such as this may be found below. These are further illustrated in Chinese Journal of Chemistry, 27(1), 33-42; 2009; WO 09/049846; Journal of Antibiotics, 61(10), 603-614; 2008; Bioorganic & Medicinal Chemistry Letters, 18(24), 6471-6475; 2008; Journal of Medicinal Chemistry, 51(15), 4601-4608; 2008; WO 06/123145, Archiv der Pharmazie (Weinheim, Germany), 340(4), 202-208; 2007;
Synthetic Communications, 37(7), 1155-1165; 2007; Russian Journal of Organic Chemistry, 42(5), 735-738; 2006; Bioinorganic Chemistry and Applications, 1(3-4), 299-308; 2003; Synthetic Communications, 28(14), 2621-2633; 1998; Synthetic Communications, 19(18), 3129-38; 1989. 4) Oximes of formula (la) may be obtained by a condensation reaction, whereby a compound of formula (III) is reacted with hydroxylamine, or, alternatively, with a salt of hydroxylamine. A more detailed description of condensation reactions is given below.
Related references include the following: Journal of Heterocyclic Chemistry, 46(1), 116- 118; 2009; Journal of Medicinal Chemistry, 20(5), 718-21; 1977; Journal of Organic
Chemistry, 73(11), 4017-4026; 2008; EJEAFChe, Electronic Journal of Environmental, Agricultural and Food Chemistry, 5(5), 1515-1521; 2006; Advanced Synthesis & Catalysis, 346(13-15), 1798-1811; 2004. Scheme 3
Figure imgf000093_0001
5) Alternatively, as seen in scheme 3, compounds of formula (lb), that is a compound of formula (I) wherein X is X-3, X-4 or X-5, wherein Z4, Z5, Z8, Z9, Z13 and Z14 are methylene and Z3, Z6, Z7, Z10, Z11 and Z12 (represented in the scheme collectively as X') are as defined herein for compounds of formula (I), may be prepared by catalytic hydrogenation from compounds of formula (IV) in the presence of a metal catalyst, for example palladium, nickel or platinum. The reaction is usually carried out in the presence of a solvent under a hydrogen atmosphere. In some cases it is necessary to apply pressure in the range of 1 to 100 bar. Suitable solvents for such reactions are alcohols, such as methanol or ethanol, cyclic ethers, such as dioxane or tetrahydrofuran or esters like ethyl acetate. The reaction is usually carried out at a reaction temperature ranging from 0°C to the boiling point of the solvent. Examples for the hydrogenation in the presence of a nickel catalyst can be found in Journal of Organometallic Chemistry, 333(2), 139-53; 1987. Examples for the hydrogenation in the presence of a palladium catalyst can be found in Tetrahedron, 63(26), 6015-6034; 2007 or in Bioorganic & Medicinal Chemistry, 9(11), 2863-2870; 2001. Examples for the hydrogenation in the presence of a platinum catalyst can be found in Journal of Organic Chemistry, 53(2), 386-90; 1988 or in Journal of Medicinal Chemistry, 32(8), 1820-35; 1989
6) Compounds of formula (IV) may be obtained by condensation reaction from compounds of formula (V). The reaction can be carried out analogously to procedure 2 or procedures 3 and 4 as shown in Scheme 2.
7) Alternatively, as seen in scheme 3, compounds of formula (lb) may be obtained from compounds of formula (Ilia). The reaction can be carried out analogously to procedure 2 or procedures 3 and 4 as shown in Scheme 2.
8) Compounds of formula (Ilia) may be obtained from compounds of (V) by catalytic hydrogenation. The reaction can be carried out analogously to procedure 5 as shown in Scheme 3.
Scheme 4:
Figure imgf000094_0001
Figure imgf000094_0002
9) Alternatively, as seen in scheme 4, compounds of formula (Ic), that is a compound of formula I wherein Z3, Z6, Z7, Z10, Z11 and Z12 are as defined herein for compounds of formula (I) (depicted in the scheme as X7); CHR23 represents Z4, Z8 or Z13; CHR24 represents Z5, Z9 or Z14; R23 and R24 independently of one another represent hydrogen, halogen, Q- i alkyl, Ci-d haloalkyl, phenyl or CN, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, d-d alkyl, d-d haloalkyl, Crd alkoxy and d-d haloalkyoxy, may be prepared by catalytic hydrogenation from compound (VI) in the presence of a metal catalyst like for example palladium, nickel or platinum. The reaction is usually carried out in the presence of a solvent under a hydrogen atmosphere. In some cases it is necessary to apply pressure in the range of 1 to 100 bar. Suitable solvents for such reactions are alcohols, such as methanol or ethanol, cyclic ethers, such as dioxane or tetrahydrofuran or esters like ethyl acetate. The reaction is usually carried out at a reaction temperature ranging from 0°C to the boiling point of the solvent.
Examples for the hydrogenation in the presence of a nickel catalyst can be found in Journal of Organic Chemistry, 69(6), 1959-1966; 2004. Examples for the hydrogenation in the presence of a palladium catalyst can be found in Journal of Organic Chemistry, 74(16), 6072-6076; 2009. Examples for hydrogenation in the presence of a platinum catalyst can be found in Organometallics, 5(2), 348-55; 1986.
10) Compounds of formula (VI) may be obtained by condensation reaction from compounds of formula (VII). The reaction can be carried out analogously to procedure 2 or procedures 3 and 4 as shown in Scheme 2.
11) Alternatively, as seen in scheme 4, compounds of formula (Ic) may be obtained from compounds of formula (Illb), that is a compound of formula (III) wherein Z3, Z6, Z7, Z10, Z11 and Z12 are as defined herein for compounds of formula (I) (depicted in the scheme as X'); CHR23 represents Z4, Z8 or Z13; CHR24 represents Z5, Z9 or Z14; R23 and R24
independently of one another represent hydrogen, halogen, Ci- alkyl, Ci-d haloalkyl, phenyl or CN, wherein phenyl is optionally substituted by one or more groups, e.g. one to five groups, independently selected from halogen, CN, Crd alkyl, Crd haloalkyl, Crd alkoxy and Crd haloalkyoxy. The reaction can be carried out analogously to procedure 2 or procedures 3 and 4 as shown in Scheme 2.
12) Compounds of formula (Illb) may be obtained from compounds of (VII) by catalytic hydrogenation. The reaction can be carried out analogously to procedure 9 as shown in Scheme 4.
Figure imgf000096_0001
13) Alternatively, as seen in scheme 5, compounds of formula (Id), that is a compound of formula (I) wherein Z5, Z9 or Z14 represent C=CR17R18 (Z3, Z4, Z6, Z7, Z8, Z10, Z11, Z12 and Z13 are depicted by X" in the scheme) may be obtained from compounds of formula (Hid), that is a compound of formula (III) wherein Z6, Z9 or Z14 represent C=CR17R18 (Z3, Z4, Z6, Z7, Z8, Z10, Z11, Z12 and Z13 are depicted by X" in the scheme). The reaction can be carried out analogously to procedures procedure 2 or procedures 3 and 4 as shown in Scheme 2. In certain cases it may be appropriate to deprotect the ketone function first to obtain compounds of formula (XXIII) wherein X" represents
#-z3-Z4-# #_Z6_ Z7_Z8_# #_zio_z!i_zi2_z!3_#
X"-1 X"-2 X"-3
D1, D2, A, R1, R17, R18, Y1, Y2, Y3, Z3, Z4, Z6, Z7, Z8, Z10, Z11, Z12 and Z13 are as defined for a compound of formula (I).
14) Compounds of formula (Hid) may be obtained from compounds of (IIIc), that is a compound of formula (III) wherein Z5, Z9 or Z14 represent C=0 (Z3, Z4, Z6, Z7, Z8, Z10, Z11, Z12 and Z13 are depicted by X" in the scheme). This can be done using one of several techniques well known to the person skilled in the art, including Wittig reaction or condensation reactions. The Wittig reaction comprises the reaction between an aldehyde or a ketone, for instance the ketone of formula (IIIc), and a phosphorous ylide. Phosphorous ylides are usually prepared by treatment of a phosphonium salt with a base and phosphonium salts are usually prepared from a triarylphosphine and an alkyl halide. Several improvements and modification of the Wittig reaction are known and are described in the literature well known to the person skilled in the art, for example in March's Advanced Organic Chemistry:
Reaction, Mechanisms and Structure, Sixth Edition, 2007 and references therein. Specific reaction conditions may be found in Journal of the American Chemical Society, 131(34), 12344-12353; 2009; Journal of Medicinal Chemistry, 51(22), 7193-7204; 2008 or Journal of Organic Chemistry, 74(11), 4166-4176; 2009.
Scheme 6:
Figure imgf000097_0001
15) Compounds of formula (Ila), that is a compound of formula (II) wherein Z4, Z5, Z8, Z9, Z13 and Z14 represent methylene (Z3, Z6, Z7, Z10, Z11 and Z12 are depicted by X' in the scheme) may be obtained from compounds of (VIII) by cleavage of the phthalimide protecting group. Examples for such deprotections can be found in Greene, T. W., Wuts, P. G. N., Protective Groups in Organic Synthesis, John Wiley & Sons, Inc, 2006.
16) Compounds of formula (VIII) may be obtained by catalytic hydrogenation from compounds of formula (IX). The reaction may be carried out analogously as shown in
Scheme 3 for procedure 5.
17) Compounds of formula (IX) may be prepared from compounds of formula (X) by a Mitsunobu reaction. The Mitsunobu reaction comprises the substitution of primary or secondary alcohols with nucleophiles, for example N-hydroxyphthalimide, as seen in
Scheme 6, in the presence of a dialkyi azodicarboxylate and a trialkyl- or triaryl phosphine. Several improvements and modifications of the Mitsunobu reaction are known and are described in the literature and are well known to the person skilled in the art, for example in March's Advanced Organic Chemistry: Reaction, Mechanisms and Structure, Sixth Edition, 2007 and references therein. Specific reaction conditions may be found in Organic
Preparations and Procedures International, 26(1), 111-13; 1994; Organic Letters, 11(9), 5 2019-2022; 2009; Tetrahedron Letters, 48(4), 647-650; 2007 or Journal of Organic
Chemistry, 70(17), 6995-6998; 2005
Scheme 7:
Figure imgf000098_0001
(XXIV) (XXV) (III)
0
(18) Compounds of formula (III) may be prepared by reacting compounds of formula
(XXV) wherein D1, D2, X, Y1, Y2 and Y3 and R1 are as defined herein for compounds of formula (I) and T1 and T2 are Ci-C8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-Ci-C6-5 alkylidene-O) whereby the alkylidene fragment may optionally be mono- to tetra-substituted by Ci-C6 alkyl and R27 is a halogen, in particular chlorine, bromine or iodine, or a sulfonic acid ester group, such as mesylate, tosylate, triflate, phenylsulfonic acid ester, nitro- phenylsulfonic acid ester, or nonafluorobutylsulfonic acid ester and a compound of formula
(XXVI) wherein A and R1 are as defined herein for compounds of formula (I). The alkylation0 reaction can be carried out analogously to procedure 3 as shown in Scheme 1.
(19) Compounds of formula (XXV) can be prepared from compounds of formula (XXIV), wherein D1, D2, X, Y1, Y2 and Y3 and R1 are as defined herein for compounds of formula (I) and T1 and T2 are Q-C8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC6-alkylidene-0)5 whereby the alkylidene fragment may optionally be mono- to tetra-substituted by CrC6 alkyl. Such transformations can be affected using a number of conditions well known to the person skilled in the art. Scheme 8:
Figure imgf000099_0001
(XI) (V)
(20) Compounds of formula (V) may be prepared from compounds of formula (XI) and compounds of formula (XXVI). The alkylation reaction can be carried out analogously as shown in Scheme 1 for procedure 3.
(21) Compounds of formula (XI) can be prepared from compounds of formula (XIII). Such transformations can be effected using a number of conditions well known to the person skilled in the art.
(22) Alternatively as seen in Scheme 8 compounds of (V) may be prepared by a
Sonogashira reaction of compounds of formula (XXVII) wherein R26 is CI, Br, I or a sulfonate; T1 and T2 are Q-C8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC6-alkylidene-0) whereby the alkylidene fragment may optionally be mono- to tetra-substituted by CrC6 alkyl; and D1, D2, Y1, Y2, Y3 and R1 are as defined herein for compounds of formula (I) with compounds of formula (XII). The reaction can be carried out in the presence of a palladium catalyst, for example tetrakis triphenyphosphine palladium (0) or dichlorobis (triphenylphosphine) palladium(II), a copper(I) salt like copper (I) chloride; copper (I) bromide or copper (I) iodide and a base, for example triethylamine, ethyldiisopropylamine, diethylamine, diisopropylamine or dicyclohexylamine. Where possible, the base may also serve as solvent. Examples for other suitable solvents are Ν,Ν-dimethylformamide, N,N-dimethylacetamide, acetonitrile, dimethylsulfoxide, dioxane or tetrahydrofuran. The reaction is usually carried out at a reaction temperature ranging from 0°C to the boiling point of the solvent. Examples of Sonogashira reactions can be found in Handbook of Organopalladium Chemistry for Organic Synthesis 2002,1, 493-529.
(23) Compounds of formula (XII) may be prepared by an alkylation reaction from compounds of formula (XXVI) and compounds of (XXVIII) wherein X' represents X'-l, X'-2 or X'-3
#—∑—# #—∑—∑—# #—∑—∑—∑—#
X'-1 X'-2 X'-3
Z3, Z4, Z6, Z7, Z10, Z11 and Z12 are as defined herein for a compound of formula (I);
and R25 is a halogen, in particular chlorine, bromine or iodine, or a sulfonic acid ester group, such as mesylate, tosylate, triflate, phenylsulfonic acid ester, nitro-phenylsulfonic acid ester, or nonafluorobutylsulfonic acid ester. Many of such compounds (XXVIII) are known in the literature and are commercially available or can be prepared by methods well known to the person skilled in the art.
Scheme 9:
Figure imgf000100_0001
(24) Compounds of formula (XIII) may be prepared by a Sonogashira reaction from compounds of formula (XXIX) wherein X' represents X'-l, X'-2 or X'-3
#—∑—# #—∑—∑—# #—∑—∑—∑—#
X'-1 X'-2 X'-3
Z3, Z4, Z6, Z7, Z10, Z11 and Z12 are as defined herein for a compound of formula (I);
and compounds of (XXVII). The Sonogashira reaction can be carried out analogously to procedure 22 as shown in Scheme 8.
Figure imgf000101_0001
(25) Compounds of formula (XIV) may be prepared from compounds of formula (XV) and compounds of formula (XXVI). The alkylation reaction can be carried out analogously to procedure 3 as shown in Scheme 2.
(26) Compounds of formula (XV) may be prepared from compounds of formula (XVI) in a multistep synthesis. This can be done using one of several techniques well known to the person skilled in the art, including Wittig reaction or Horner- Wad sworth Emmons reactions in the first step and further transformations as seen in Scheme 11.
cheme 11:
Figure imgf000102_0001
(27) Compounds of formula (XVII) may be prepared from compounds of formula (XVIII). Such transformations can be effected using a number of conditions well known to the person skilled in the art.
(28) Compounds of formula (XVIII) may be prepared from compounds of formula (XIX) by reduction with a metal hydride, for example lithium aluminium hydride or diisobutyl aluminium hydride. Examples for such reductions can found in Journal of Combinatorial Chemistry, 7(6), 958-967; 2005. The reaction is usually carried out at temperatures between -100 to 20°C in the presence of a solvent.
(29) Compounds of formula (XIX) can be prepared from compounds of formula (XVI) and a phosphonate of formula (XXX) wherein R29 and R30 are CrC4 alkyl using a Horner- Wadsworth Emmons reaction. The reaction is carried out in the presence of a base.
Appropriate bases are for example metal hydrides like calcium, lithium, sodium or potassium hydride, organometal compounds like buthyllithium or organic bases like for example triethylamine or ethyldiisopropylamine in combination with lithium chloride. Examples can be found in Bioorganic & Medicinal Chemistry, 11(18), 4015-4026; 2003; Synthesis, (4), 283-5; 1981 or in Journal of Medicinal Chemistry, 53(3), 1200-1210; 2010 Scheme 12:
Figure imgf000103_0001
(llle)
(30) Compounds of formula (Hie), that is a compound of formula (III) wherein Z2, Z5, Z9 5 and Z14 represent CR15R16 wherein R15 represents H and R16 represents OH (Z1, Z3, Z4, Z6, Z7, Z8, Z10, Z11, Z12 and Z13 are depicted by X" in the scheme) may be prepared from aldehydes of formula (XXXIII) and compounds of formula (XXXIV) wherein R31 is chlorine, bromine or iodine and D1, D2, Y3, R1, T1 and T2 are as defined for a compound of formula (III). Such a transformation may be performed by halogen metal exchange in compound (XXXIV) with an 10 appropriate reagent like for example magnesium, isopropyl magnesium chloride, or n- buthyllithium and the reaction of this metalated pyridine intermediate with a compound of formula (XXXIII) wherein X" represents
X"-l, X"-2, X"-3 or X"-4
#— z— # #— z— z4— # #— z— z— z— # #— z— z— z— z— #
X"-1 X"-2 X"-3 X"-
15 wherein A, Z1, Z3, Z4, Z6, Z7, Z8, Z10, Z11, Z12 and Z13are as defined herein for compounds of formula (I);
Examples for such transformations can be found in Angewandte Chemie, International Edition, 43(25), 3333-3336; 2004; Organic Letters, 6(26), 4905-4907; 2004; Journal of the American Chemical Society, 130(38), 12592-12593; 2008 or in Organic Letters, 11(20), 20 4540-4543; 2009
Compounds of formula (Hie) are especially useful as intermediates to a number of other compounds, wherein the hydroxy group formed is transformed into other functional groups, for example acid halides. Such transformations can be effected using a number of conditions well known to the person skilled in the art. (31) Compounds of formula (XXXIII) may be prepared by oxidation from compounds of formula (XXXII). Such oxidations can be affected using a number of conditions well known to the person skilled in the art. Specific reaction conditions may be found in Organic &
Biomolecular Chemistry, 6(21), 4036-4040; 2008; Bioorganic & Medicinal Chemistry Letters, 19(13), 3627-3631; 2009; Chemical Communications (Cambridge, United Kingdom), (37), 5618-5620; 2009; or in Synthesis, (1), 91-97; 2010.
(32) Compounds of formula (XXXII) may be prepared from compound of formula (XXVI) and compounds of formula (XXXI) wherein X" represents
X"-l, X"-2 , X"-3 or X"-4
#—∑—# #— z3— z— # #— z6— z— z8— # #— z— z— z— z— #
X"-1 X"-2 X"-3 X"- wherein Z1, Z3, Z4, Z6, Z7, Z8, Z10, Z11, Z12 and Z13are as defined herein for compounds of formula (I);
and R25 is a halogen, in particular chlorine, bromine or iodine, or a sulfonic acid ester group, such as mesylate, tosylate, triflate, phenylsulfonic acid ester, nitro-phenylsulfonic acid ester, or nonafluorobutylsulfonic acid ester. Many of such compounds are known in the literature and are commercially available or can be prepared by methods well known to the person skilled in the art. The alkylation reaction can be carried out analogously to procedure 3 as shown in Scheme 2. Schem
Figure imgf000104_0001
(XXa)
33) Oximes of formula (XXXV) may be obtained by a condensation reaction, whereby a compound of formula (XXa), that is a compound of formula XX wherein R27 represents A-9 and T1 and T2 together with the carbon they are attached to form a carbonyl group is reacted with hydroxylamine, or, alternatively, with a salt of hydroxylamine. A more detailed description of condensation processes is given below.
Related references include the following: Journal of Heterocyclic Chemistry, 46(1), 116- 118; 2009; Journal of Medicinal Chemistry, 20(5), 718-21; 1977; Journal of Organic
Chemistry, 73(11), 4017-4026; 2008; EJEAFChe, Electronic Journal of Environmental, Agricultural and Food Chemistry, 5(5), 1515-1521; 2006; Advanced Synthesis & Catalysis, 346(13-15), 1798-1811; 2004.
Some compounds of formula (XXa) are known and their preparation has been published or they are available commercially. A few typical examples are given in Table 35 together with the corresponding CAS numbers. Analogous protocols to those used to prepare the following compounds can be used to prepare other compounds of formula (XXa).
Table 35
Figure imgf000105_0001
Figure imgf000106_0001
Scheme 14
Figure imgf000106_0002
(xxxvi) (xxxv)
34) Alternatively, oximes of formula (XXXV) can be obtained by a nitrosation reaction of compounds of formula (XXXVI), wherein G1, G2, G3, p, R4, R5 and R6 are as defined herein for compounds of formula (I), with base and an alkyl nitrite, as seen in scheme 14. Typical bases include lithium diisopropyl amide (LDA), lithium hexamethyldisilazane, n-butyl lithium, s-butyl lithium, tert-butyl lithium, sodium tert-butylate or potassium tert-butylate. Typical alkyl nitrites include isopentyl nitrite and tert-butyl nitrite. The compound of formula (XI), the alkyl nitrite or the base can be used in different stoichiometric amounts, with each reagent possibly being in excess with respect to the others. Preferentially, such reactions are carried out under non-aqueous conditions in an inert solvent such as hexane, heptanes,
cyclohexane, toluene or ethers such as THF or tert-butyl methyl ether. The reaction may be performed at temperatures ranging from -80 to 250°C, preferably between -50 and 120°C.
Such reactions can lead to a mixture of the E- and the Z-oxime (ether) product, or the product may also be exclusively either the E- or the Z-oxime (ether).
A large number of these types of transformations are known in the art. Typical reaction conditions for this type of reaction may be found in Crawford, Jason B.; Chen, Gang;
Gauthier, David; Wilson, Trevor; Carpenter, Bryon; Baird, Ian R.; McEachern, Ernie; Kaller, Alan; Harwig, Curtis; Atsma, Bern; Skerlj, Renato T.; Bridger, Gary 1, Organic Process Research & Development (2008), 12(5), 823-830, McEachern, E. 1; Yang, W.; Chen, G.; Skerlj, R. T.; Bridger, G. 1, Synthetic Communications (2003), 33(20), 3497-350; and Bark, Thomas; Thummel, Randolph P., Inorganic Chemistry (2005), 44(24), 8733-8739. Ketone intermediates of formula XXb, that is a compound of formula XX wherein R27 is A-10 and T1 and T2 together with the carbon they are attached to form a carbonyl group; XXc, that is a compound of formula XX wherein R27 is A-7 and T1 and T2 together with the carbon they are attached to form a carbonyl group; XXd, that is a compound of formula XX wherein R27 is A and T1 and T2 together with the carbon they are attached to form a carbonyl group -8 may be prepared by a variety of methods, illustrated in schemes 15-17.
Figure imgf000107_0001
XXb
Some compounds of formula (XXb) are known and their preparation has been published or they are available commercially. A few typical examples are given in Table 36 together with the corresponding CAS numbers. Table 36
Figure imgf000108_0002
Scheme 15
Figure imgf000108_0001
35) Compounds of formula (XXb) can be obtained by acidic hydrolysis methods, well known to the person skilled in the art of compounds of formula (L), wherein G1, G2, G3, p, R4 and R5 are as defined herein for compounds of formula (I) and R28 is alkyl.
37) Enolethers of formula (L) can be obtained by reacting enaminone of formula (LI) wherein G1, G2, G3, p, R4 and R5 are as defined herein for compounds of formula (I) and R28 is alkyl with amidines or guanidines of formula (LII) wherein R5 is a defined for compounds of formula (I). Such condensation reactions can be performed using a number of conditions well known to the person skilled in the art. Such reactions are carried out in the presence of a base preferentially sodium or potassium alcoholate in ethanol or methanol. Specific reaction conditions may be found in Synthesis, 1012-1018, 1996; J. Heterocycl. Chem. 20, 649-653, 1983 or in WO2009010488.
38) Enaminone of formula (LI) can be obtained by reacting ketone of formula (LIII) wherein G1, G2, G3 and p are as defined herein for compounds of formula (I) and R28 is alkyl
5 with Ν,Ν-dimethylformamide dialkyl acetal of formula (LIV) wherein R29 is alkyl. Such condensation reactions are well known to the person skilled in the art. The reaction is carried out in an inert solvent or without solvent at temperatures ranging from 0°C to 250°C, preferably between 50 and 160°C. Specific reaction conditions may be found in Synthesis, (97), 3397, 1964; Synthesis, (97), 3407, 1964; Journal of Med. Chem., Vol. 52, No. 16, 10 5152-5163; Tetrahedron Lett, (27), 2567, 1986; Tetrahedron Lett, (50), 2255-2264, 1994;
Synthetic Commun., (28), 10, 1743-1753, 1998 or in Chem. Ber., (104), 2975, 1971.
39) Enol ether of formula (LIII) can be obtained by reacting ketones of formula (LVI) wherein G1, G2, G3 and p are as defined herein for compounds of formula (I) with an alcohol of formula (LVII) wherein R28 is alkyl. Such enol reactions can be affected using a number of
15 conditions well known to the person skilled in the art. Specific reaction conditions may be found in WO2004104007.
Figure imgf000109_0001
XXd
Some compounds of formula (XXc) or (XXd) are known and their preparation has been 20 published or they are available commercially. A few typical examples are given in Table 37 together with the corresponding CAS numbers.
Table 37
Figure imgf000109_0002
Figure imgf000110_0001
Scheme 16
Figure imgf000110_0002
(LX) (LXII) XXdi 40) Ketone intermediates of formula (XXci) or (XXdi), that is compounds of formula XXc and XXd wherein R3 is methyl can be obtained by a Stille cross-coupling reaction of the halo pyrimidine derivative of formula (LX) wherein X1 is a halogen, preferably chlorine or bromine and R4, R5 and R6 are as defined for compounds of formula (I) with tri-/7-butyl(l- ethoxyvinyl)tin (LXI) wherein R30 is alkyl to give the vinyl ether of formula (LXII), wherein R4, R5 and R6 are as defined for compounds of formula (I) and R30 is alkyl which by acidic hydrolysis methods give the desired ketone intermediate of formula (XXc) or (XXd).
Examples for such Stille cross-coupling reaction can be found in Angew. Chem. Int. Ed.
Engl., 25, 508—524 (1986); Bull. Chem Soc. Jpn. 60, 767, 1987; Tetrahedron, 45, 993— 1006 (1989); Acta Chem. Scand, 43, 62—68 (1989); Tetrahedron (1996), 52(15), 5625-38 or Angewandte Chemie, International Edition (2002), 41(7), 1195-1198.
Scheme 17
Figure imgf000111_0001
(LX) (LXIII) XXd
41) Alternatively compounds of formula (LX) can be converted to the corresponding nitrile of formula (LXIII) wherein R4, R5, R6 and R7 are as defined for compounds of formula (I) by well known standard procedures. A subsequent reaction of nitrile derivative of formula (LXII) with a Grignard reagent of the formula R3-MgBr, wherein R3 is as defined under formula IIA, yields the ketone intermediate of formula (XX A-2) or (XX A-3) as described in scheme 17.
Typical conditions for condensation reactions:
This applies to procedures 1, 2, 4, 6, 7, 10, 11, 13.
Different stoichiometric set-ups may be used for these reactions, depending on the properties of reactants and product. An excess of the electrophile, the nucleophile, or equimolar amounts may be chosen. Preferentially equimolar amounts of electrophilic and nucleophilic compounds are used.
The reaction may be performed in the presence or absence of an inert organic or inorganic solvent, or in the presence of a mixture of such solvents. Preferentially, it is performed in the presence of one or more solvents. Preferred solvents include the following aliphatic or aromatic hydrocarbons, which may optionally be substituted by one or more halogen atoms, such as pentane, hexanes, heptanes, cyclohexane, petroleum ether, benzene, toluene, xylene, chlorobenzene, dichlorobenzenes, dichloromethane, chloroform, 1,2-dichloroethane or carbon tetrachloride, ethers such as diethylether, diisopropyl ether, tert-butyl methyl ether, tetrahydrofuran, 1,4-dioxane, dimethoxyethane or diglycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone, acids and ester such as acetic acid, ethyl acetate or methyl acetate, aprotic polar solvents such as acetonitrile, pripionitril, dimethyl formamide, dimethyl acetamide, N- methyl-pyrrolidone, dimethyl sulfoxide, sulfolane, DMPU, or pyridine and picolines. The selection of solvents includes water and alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, isopentanol, hexanol, trifluorethanol, ethylene glycol or methoxyethanol.
The reaction may be performed between -20 C and 250 C, preferentially between 0°C and lOO C. In some cases the reaction mixture may be heated to reflux.
Where appropriate, compounds can be used in the form of the free compound, or, alternatively, they can be used in the form of a salt such as the acetate, trifluoroacetate, propionate, benzoate, oxalate, methyl solfonate, phenylsulfonate, p-tolylsulfonate, trifluormethylsulfonate, fluoride, chloride, bromide, iodide, sulphate, hydrogensulphate or nitrate, including bis-salts if appropriate.
The reaction can be carried out in the absence of an acid using the free compounds. Alternatively, the reaction may be performed in the presence of an acid in catalytic, stoichiometric or excess amounts. Acids that could be used include acetic acid, propionic acid, oxalic acid, trifluoroacetic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, methansulfonic acid, para-toluenesulfonic acid, sulphuric acid, sodium hydrogensulphate and phosphoric acid. The reaction can optionally be carried out in a water-free solvent system in the presence of a drying agent, such as sodium or magnesium sulphate, potassium carbonate or molecular sieves.
If the two substituents at the carbon atom of the oxime or oxime ether function are different from each other, the condensation reaction can lead to a mixture of the E- and the Z-oxime (ether) product. The condensation product may also be exclusively either the E- or the Z- oxime (ether).
Condensations can be performed under reduced pressure, normal pressure or increased pressure. Preferentially the reaction is performed under normal pressure.
Typical conditions for alkylation reactions:
This applies to procedure 3, 18, 20, 25, 32.
Different stoichiometric set-ups may be used for these reactions, depending on the properties of reactants and product. An excess of the electrophile, the nucleophile, or neither may be chosen. Usually, it is preferable that equimolar amounts of electrophilic and nucleophilic compounds are used.
The reaction may be performed in the absence or presence of a solvent or a mixture of solvents. Preferential solvents include the following aliphatic or aromatic hydrocarbons that may optionally be substituted by one or more halogen atoms such as pentane, hexanes, heptanes, cyclohexane, petroleum ether, benzene, toluene, xylene, chlorobenzene, dichlorobenzenes, dichloromethane, chloroform, 1,2-dichloroethanev or carbon tetrachloride, ethers such as diethyl ether, diisopropyl ether, tert-butyl-methyl ether, tetrahydrofuran, 1,4- dioxane, dimethoxyethane or diglycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone, acids and ester such as acetic acid, ethyl acetate or methyl acetate, aprotic polar solvents such as acetonitrile, pripionitrile, dimethyl formamide, dimethyl acetamide, N-methyl-pyrrolidone, dimethyl sulfoxide, sulfolane, DMPU, or pyridine and picolines. The selction of solvents includes also water and alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, isopentanol, hexanol, trifluorethanol, ethylene glycol or methoxyethanol.
The reaction may be performed in a biphasic system comprising an organic solvent that is not miscible with water, such as toluene, dichloromethane, dichloro-ethylene, and an aqueous solvent, such as water. Such a reaction would be performed in the presence of a phase-transfer catalyst, such as tetra-n-butylammonium bromide (TBAB),
Tetradecyldimethylbenzylammonium chloride (TDMBAC), N-Benzyltrimethylammonium hydroxide, along with aqueous sodium or potassium hydroxide in stoichiometric amounts. The biphasic reaction may be performed with or without ultrasonication.
The reaction may be carried out at temperatures varying from -100°C and 250°C.
Preferentially, the temperature range is between 0°C and 100°C.
Optionally, an organic or inorganic base may be present such as alkali- and earth alkali acetates, amides, carbonates, hydrogencarbonates, hydrides, hydroxides or alcoholates such as sodium, potassium, caesium or calcium acetate, sodium, potassium, caesium or calcium carbonate, sodium, potassium, caesium or calcium hydrogencarbonate, sodium, potassium, caesium or calcium hydride, sodium, potassium, caesium or calcium amide, sodium, potassium, caesium or calcium hydroxide, sodium, potassium, caesium or calcium
methanolate, sodium, potassium, caesium or calcium ethanolate, sodium, potassium, caesium or calcium n-, i-, s- or t-butanolate, triethylamine, tri propylamine, tributylamine, di- isopropyl-ethylamine, Ν,Ν-dimethyl-cyclohexylamine, N-methyl-dicyclohexylamine, N,N- di methyl-aniline, N,N-diethyl-aniline, Ν,Ν-dimethyl-benzylamine, N,N-diethyl-benzylamine, pyridine, 2-methyl-pyridine, 3-methyl-pyridine, 4-methyl-pyridine, 2,6-dimethyl-pyridine, 2,4,6-trimethyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, N-ethyl-piperidine, N-methyl-morpholine, N-ethyl-morpholine, N,N'-dimethyl-piperazine, 1,4- Diazabicyclo[2.2.2]octane (DABCO), l,8-Diaza-7-bicyclo[5.4.0]undecene (DBU), 1,5- Diazabicyclo[4.3.0]non-5-ene (DBN), l-tert-Butyl-2,2,2-tri(l-pyrrolidinyl)phosphazene (BTPP), l-tert-Butyl-2,2,2-tris(dimethylamino)phosphazene, sodium hexamethyldisilazane, potassium hexamethyldisilazane, lithium diisopropylamide, ethyl magnesium chloride, isopropylmagnesium chloride.
The alkylation can be performed under reduced pressure, normal pressure or increased pressure. Preferentially the reaction is performed under normal pressure.
The products of steps 1) to 31) may be required to be purified using, for example, chromatography, crystallisation or other purification techniques well known to the person skilled in the art.
The compounds of formula (I) to formula (XXXIV) and, where appropriate, the tautomers thereof, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
It has now been found that the compounds of formula (I) according to the invention have, for practical purposes, a very advantageous spectrum of activities for protecting useful plants against diseases that are caused by phytopathogenic microorganisms, such as fungi, bacteria or viruses.
The invention therefore also relates to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a compound of formula (I) is applied as active ingredient to the plants, to parts thereof or the locus thereof. The compounds of formula (I) according to the invention 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 useful plants. The compounds of formula (I) can be used to inhibit or destroy the diseases 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 of formula (I) according to the 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 or in hygiene management.
The compounds of formula (I) are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes classes (e.g. Phytophthora, Pythium, Plasmopara). Within the scope of the invention, useful plants 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 term "useful plants" is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®.
The term "useful plants" is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrvIIIB(bl) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CryIF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton 5 variety that expresses a CrylA(c) and a CryllA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CrylllA toxin); Nature- Gard® Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Btll corn borer (CB) trait), Agrisure® RW (corn rootworm trait) and Protecta®.
The term "useful plants" is to be understood as including also useful plants which have
10 been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353
15 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
The term "locus" of a useful plant as used herein is intended to embrace the place on which the useful plants are growing, where the plant propagation materials of the useful plants are sown or where the plant propagation materials of the useful plants will be placed
20 into the soil. An example for such a locus is a field, on which crop plants are growing.
The term "plant propagation material" is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants.
25 Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. Preferably "plant propagation material" is understood to denote seeds.
The compounds of formula (I) can be used in unmodified form or, preferably, together
30 with carriers and adjuvants conventionally employed in the art of formulation.
Therefore the invention also relates to compositions for controlling and protecting against phytopathogenic microorganisms, comprising a compound of formula (I) and an inert carrier, and to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a composition, comprising a compound of formula
35 (I) as active ingredient and an inert carrier, is applied to the plants, to parts thereof or the locus thereof. To this end compounds of formula (I) and inert carriers 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 (auxiliaries) can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890.
The compounds of formula (I) or compositions, comprising a compound of formula (I) as active ingredient and an inert carrier, can be applied to the locus of the plant 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.
A preferred method of applying a compound of formula (I), or a composition, comprising a compound of formula (I) as active ingredient and an inert carrier, 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) may also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field. The compounds of formula (I) may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
A formulation, i.e. a composition comprising 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.
Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.
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 rates of application are from lOmg to lg of active substance per kg of seeds. The rate of application for the desired action can be determined by experiments. It depends for example on the type of action, the developmental stage of the useful plant, and on the application (location, timing, application method) and can, owing to these parameters, vary within wide limits.
The compounds of formula (I), or a pharmaceutical salt thereof, described above may also have an advantageous spectrum of activity for the treatment and/or prevention of microbial infection in an animal. "Animal" can be any animal, for example, insect, mammal, reptile, fish, amphibian, preferably mammal, most preferably human. "Treatment" means the use on an animal which has microbial infection in order to reduce or slow or stop the increase or spread of the infection, or to reduce the infection or to cure the infection.
"Prevention" means the use on an animal which has no apparent signs of microbial infection in order to prevent any future infection, or to reduce or slow the increase or spread of any future infection.
According to the present invention there is provided the use of a compound of formula (I) in the manufacture of a medicament for use in the treatment and/or prevention of microbial infection in an animal. There is also provided the use of a compound of formula (I) as a pharmaceutical agent. There is also provided the use of a compound of formula (I) as an antimicrobial agent in the treatment of an animal. According to the present invention there is also provided a pharmaceutical composition comprising as an active ingredient a compound of formula (I), or a pharmaceutically acceptable salt thereof, and a
pharmaceutically acceptable diluent or carrier. This composition can be used for the treatment and/or prevention of antimicrobial infection in an animal. This pharmaceutical composition can be in a form suitable for oral administration, such as tablet, lozenges, hard capsules, aqueous suspensions, oily suspensions, emulsions dispersible powders, dispersible granules, syrups and elixirs. Alternatively this pharmaceutical composition can be in a form suitable for topical application, such as a spray, a cream or lotion. Alternatively this pharmaceutical composition can be in a form suitable for parenteral administration, for example injection. Alternatively this pharmaceutical composition can be in inhalable form, such as an aerosol spray.
The compounds of formula (I) may be effective against various microbial species able to cause a microbial infection in an animal. Examples of such microbial species are those causing Aspergillosis such as Aspergillus fumigatus, A. flavus, A. terrus, A. nidulans and A. niger, those causing Blastomycosis such as Blastomyces dermatitidis, those causing
Candidiasis such as Candida albicans, C. glabrata, C. tropicalis, C. parapsilosis, C. krusei and C. lusitaniae, those causing Coccidioidomycosis such as Coccidioides immitis, those causing Cryptococcosis such as Cryptococcus neoformans, those causing Histoplasmosis such as Histoplasma capsulatum and those causing Zygomycosis such as Absidia corymbifera, Rhizomucor pusillus and Rhizopus arrhizus. Further examples are Fusarium Spp such as Fusarium oxysporum and Fusarium solan/ and Scedosporium Spp such as Scedosporium apiospermum and Scedosporium prolificans. Still further examples are Microsporum Spp, Trichophyton Spp, Epidermophyton Spp, Mucor Spp, Sporothorix Spp, Phialophora Spp, Cladosporium Spp, Petriellidium spp, Paracoccidioides Spp and Histoplasma Spp.
In addition, further, other biocidally active ingredients or compositions may be combined with the compound of formula (I) and used in the methods of the invention and applied simultaneously or sequentially with the compound of formula (I). When applied
simultaneously, these further active ingredients may be formulated together with the compound of formula (I) or mixed in, for example, the spray tank. These further biocidally active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.
Accordingly, in one aspect, the present invention provides a composition comprising a compound of formula (I), which is selected from the Tables 1 to 34, and (i) a further fungicide, (ii) a herbicide, (iii) an insecticide, (iv) a bactericide, (v) an acaricide, (vi) a nematicide and/or (vii) a plant growth regulator.
Additionally, the present invention provides for the use of a composition in the methods of the present invention, said composition comprising a compound of formula (I), which is selected from Tables 1 to 35, and (i) a further fungicide, (ii) a herbicide, (iii) an insecticide, (iv) a bactericide, (v) an acaricide, (vi) a nematicide and/or (vii) a plant growth regulator.
In addition, the compounds of the invention may also be applied with one or more systemically acquired resistance inducers ("SAR" inducer). SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.
The present invention relates additionally to mixtures comprising at least a compound of formula I and at least a further, other biocidally active ingredient and optionally further ingredients. The further, other biocidally active ingredient are known for example from "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition (New edition (02 Nov 2003)); Editor: C. D. S. Tomlin; The British Crop Protection Council, ISBN-10: 1901396134; ISBN-13: 978-1901396133] or its electronic version "e-Pesticide Manual V4.2" or from the website http://www.alanwood.net/pesticides/ or preferably one of the further pesticides listed below.
The following mixtures of the compounds of TX with a further active ingredient (B) are preferred (the abbreviation "TX" means a compound encompassed by the compounds of formula I, or preferably the term "TX" refers to a compound selected from the Tables 1-34 and Tables 38-39:
an adjuvant selected from the group of substances consisting of petroleum oils
(alternative name) (628) + TX,
an acaricide selected from the group of substances consisting of l,l-bis(4-chloro- phenyl)-2-ethoxyethanol (IUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate (IUPAC/Chemical Abstracts name) (1059) + TX, 2-fluoro-N-methyl-N-l-naphthylacetamide (IUPAC name) (1295) + TX, 4-chlorophenyl phenyl sulfone (IUPAC name) (981) + TX, abamectin (1) + TX, acequinocyl (3) + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, alpha-cypermethrin (202) + TX, amidithion (870) + TX, amidoflumet [CCN] + TX, amidothioate (872) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, aramite (881) + TX, arsenous oxide (882) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azobenzene (IUPAC name) (888) + TX, azocyclotin (46) + TX, azothoate (889) + TX, benomyl (62) + TX, benoxafos (alternative name) [CCN] + TX, benzoximate (71) + TX, benzyl benzoate (IUPAC name) [CCN] + TX, bifenazate (74) + TX, bifenthrin (76) + TX, binapacryl (907) + TX, brofenvalerate (alternative name) + TX, bromocyclen (918) + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX,
bromopropylate (94) + TX, buprofezin (99) + TX, butocarboxim (103) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, calcium polysulfide (IUPAC name) (111) + TX, camphechlor (941) + TX, carbanolate (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbophenothion (947) + TX, CGA 50'439 (development code) (125) + TX, chinomethionat (126) + TX, chlorbenside (959) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorfenapyr (130) + TX, chlorfenethol (968) + TX, chlorfenson (970) + TX, chlorfensulphide (971) + TX, chlorfenvinphos (131) + TX, chlorobenzilate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, clofentezine (158) + TX, closantel (alternative name) [CCN] + TX, coumaphos (174) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos (1010) + TX, cufraneb (1013) + TX, cyanthoate (1020) + TX, cyflumetofen (CAS Reg. No.: 400882-07-7) + TX, cyhalothrin (196) + TX, cyhexatin (199) + TX, cypermethrin (201) + TX, DCPM (1032) + TX, DDT (219) + TX, demephion (1037) + TX, demephion-0 (1037) + TX, demephion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-0 (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-S-methyl (224) + TX, demeton-S- methylsulphon (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diazinon (227) + TX, dichlofluanid (230) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicofol (242) + TX, dicrotophos (243) + TX, dienochlor (1071) + TX, dimefox (1081) + TX, dimethoate (262) + TX, dinactin (alternative name) (653) + TX, dinex (1089) + TX, dinex- diclexine (1089) + TX, dinobuton (269) + TX, dinocap (270) + TX, dinocap-4 [CCN] + TX, dinocap-6 [CCN] + TX, dinocton (1090) + TX, dinopenton (1092) + TX, dinosulfon (1097) + TX, dinoterbon (1098) + TX, dioxathion (1102) + TX, diphenyl sulfone (IUPAC name) (1103) + TX, disulfiram (alternative name) [CCN] + TX, disulfoton (278) + TX, DNOC (282) + TX, dofenapyn (1113) + TX, doramectin (alternative name) [CCN] + TX, endosulfan (294) + TX, endothion (1121) + TX, EPN (297) + TX, eprinomectin (alternative name) [CCN] + TX, ethion (309) + TX, ethoate-methyl (1134) + TX, etoxazole (320) + TX, etrimfos (1142) + TX, fenazaflor (1147) + TX, fenazaquin (328) + TX, fenbutatin oxide (330) + TX,
fenothiocarb (337) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fen- pyroximate (345) + TX, fenson (1157) + TX, fentrifanil (1161) + TX, fenvalerate (349) + TX, fipronil (354) + TX, fluacrypyrim (360) + TX, fluazuron (1166) + TX, flubenzimine (1167) + TX, flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1169) + TX, flufenoxuron (370) + TX, flumethrin (372) + TX, fluorbenside (1174) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1192) + TX, formparanate (1193) + TX, gamma-HCH (430) + TX, glyodin (1205) + TX, halfenprox (424) + TX, heptenophos (432) + TX, hexadecyl cyclopropanecarboxylate (IUPAC/Chemical Abstracts name) (1216) + TX, hexythiazox (441) + TX, iodomethane (IUPAC name) (542) + TX, isocarbophos (alternative name) (473) + TX, isopropyl 0-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, lindane (430) + TX, lufenuron (490) + TX, malathion (492) + TX, malonoben (1254) + TX, mecarbam (502) + TX, mephosfolan (1261) + TX, mesulfen (alternative name) [CCN] + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methidathion (529) + TX, methiocarb (530) + TX, methomyl (531) + TX, methyl bromide (537) + TX, metolcarb (550) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, monocrotophos (561) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naled (567) + TX, NC-184 (compound code) + TX, NC-512 (compound code) + TX, nifluridide (1309) + TX, nikkomycins (alternative name) [CCN] + TX, nitrilacarb (1313) + TX, nitrilacarb 1: 1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250
(compound code) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, parathion (615) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, phenkapton (1330) + TX, phenthoate (631) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosphamidon (639) + TX, phoxim (642) + TX, pirimiphos-methyl (652) + TX, polychloroterpenes (traditional name) (1347) + TX, polynactins (alternative name) (653) + TX, proclonol (1350) + TX, profenofos (662) + TX, promacyl (1354) + TX, propargite (671) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothoate (1362) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyhdaphenthion (701) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, quinalphos (711) + TX, quintiofos (1381) + TX, R-1492 (development code) (1382) + TX, RA-17 (development code) (1383) + TX, rotenone (722) + TX, schradan (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, sophamide (1402) + TX, spirodiclofen (738) + TX, spiromesifen (739) + TX, SSI-121 (development code) (1404) + TX, sulfiram (alternative name) [CCN] + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulphur (754) + TX, SZI- 121 (development code) (757) + TX, tau-fluvalinate (398) + TX, tebufenpyrad (763) + TX, TEPP (1417) + TX, terbam (alternative name) + TX, tetrachlorvinphos (777) + TX, tetradifon (786) + TX, tetranactin (alternative name) (653) + TX, tetrasul (1425) + TX, thiafenox (alternative name) + TX, thiocarboxime (1431) + TX, thiofanox (800) + TX, thiometon (801) + TX, thioquinox (1436) + TX, thuringiensin (alternative name) [CCN] + TX, triamiphos (1441) + TX, triarathene (1443) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, trifenofos (1455) + TX, trinactin (alternative name) (653) + TX, vamidothion (847) + TX, vaniliprole [CCN] and YI-5302 (compound code) + TX,
an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, crufomate (1011) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,
an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX,
a bactericide selected from the group of substances consisting of 1-hydroxy-lH-pyridine- 2-thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodicin (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargaphen (alternative name)
[CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, tecloftalam (766) + TX, and thiomersal (alternative name) [CCN] + TX,
a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX, Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis (alternative name) (33) + TX, Aphidius colemani (alternative name) (34) + TX, Aphidoletes aphidimyza (alternative name) (35) + TX, Autographa californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide (scientific name) (49) + TX, Bacillus thuringiensis Berliner (scientific name) (51) + TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51) + TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. japonensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51) + TX, Bacillus thuringiensis subsp.
tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alternative name) (53) + TX, Beauveria brongniartii (alternative name) (54) + TX, Chrysoperla carnea (alternative name) (151) + TX, Cryptolaemus montrouzieri (alternative name) (178) + TX, Cydia pomonella GV (alternative name) (191) + TX, Dacnusa sibirica (alternative name) (212) + TX, Diglyphus isaea (alternative name) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus (alternative name) (300) + TX, Helicoverpa zea NPV (alternative name) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alternative name) (433) + TX, Hippodamia convergens (alternative name) (442) + TX, Leptomastix dactylopii
(alternative name) (488) + TX, Macrolophus caliginosus (alternative name) (491) + TX, Mamestra brassicae NPV (alternative name) (494) + TX, Metaphycus helvolus (alternative name) (522) + TX, Metarhizium anisopliae var. acridum (scientific name) (523) + TX, Metarhizium anisopliae var. anisopliae (scientific name) (523) + TX, Neodiprion sertifer NPV and N. lecontei NPV (alternative name) (575) + TX, Orius spp. (alternative name) (596) + TX, Paecilomyces fumosoroseus (alternative name) (613) + TX, Phytoseiulus persimilis (alternative name) (644) + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741) + TX, Steinernema bibionis (alternative name) (742) + TX,
Steinernema carpocapsae (alternative name) (742) + TX, Steinernema feltiae (alternative name) (742) + TX, Steinernema glaseri (alternative name) (742) + TX, Steinernema riobrave (alternative name) (742) + TX, Steinernema riobravis (alternative name) (742) + TX,
Steinernema scapterisci (alternative name) (742) + TX, Steinernema spp. (alternative name) (742) + TX, Trichogramma spp. (alternative name) (826) + TX, Typhlodromus occidentalis (alternative name) (844) and Verticillium lecanii (alternative name) (848) + TX,
a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537) + TX,
a chemosterilant selected from the group of substances consisting of apholate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholate [CCN] + TX, morzid [CCN] + TX, penfluron (alternative name) [CCN] + TX, tepa [CCN] + TX, thiohempa (alternative name) [CCN] + TX, thiotepa (alternative name) [CCN] + TX, tretamine
(alternative name) [CCN] and uredepa (alternative name) [CCN] + TX,
an insect pheromone selected from the group of substances consisting of (E)-dec-5-en- 1-yl acetate with (E)-dec-5-en-l-ol (IUPAC name) (222) + TX, (E)-tridec-4-en-l-yl acetate (IUPAC name) (829) + TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541) + TX, (E,Z)- tetradeca-4,10-dien-l-yl acetate (IUPAC name) (779) + TX, (Z)-dodec-7-en-l-yl acetate (IUPAC name) (285) + TX, (Z)-hexadec-ll-enal (IUPAC name) (436) + TX, (Z)-hexadec-ll- en-l-yl acetate (IUPAC name) (437) + TX, (Z)-hexadec-13-en-ll-yn-l-yl acetate (IUPAC name) (438) + TX, (Z)-icos-13-en-10-one (IUPAC name) (448) + TX, (Z)-tetradec-7-en-l-al (IUPAC name) (782) + TX, (Z)-tetradec-9-en-l-ol (IUPAC name) (783) + TX, (Z)-tetradec-9- en-l-yl acetate (IUPAC name) (784) + TX, (7E,9Z)-dodeca-7,9-dien-l-yl acetate (IUPAC name) (283) + TX, (9Z,llE)-tetradeca-9,ll-dien-l-yl acetate (IUPAC name) (780) + TX, (9Z,12E)-tetradeca-9,12-dien-l-yl acetate (IUPAC name) (781) + TX, 14-methyloctadec-l- ene (IUPAC name) (545) + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one (IUPAC name) (544) + TX, alpha-multistriatin (alternative name) [CCN] + TX, brevicomin
(alternative name) [CCN] + TX, codlelure (alternative name) [CCN] + TX, codlemone (alternative name) (167) + TX, cuelure (alternative name) (179) + TX, disparlure (277) + TX, dodec-8-en-l-yl acetate (IUPAC name) (286) + TX, dodec-9-en-l-yl acetate (IUPAC name) (287) + TX, dodeca-8 + TX, 10-dien-l-yl acetate (IUPAC name) (284) + TX, dominicalure (alternative name) [CCN] + TX, ethyl 4-methyloctanoate (IUPAC name) (317) + TX, eugenol (alternative name) [CCN] + TX, frontalin (alternative name) [CCN] + TX, gossyplure (alternative name) (420) + TX, grandlure (421) + TX, grandlure I (alternative name) (421) + TX, grandlure II (alternative name) (421) + TX, grandlure III (alternative name) (421) + TX, grandlure IV (alternative name) (421) + TX, hexalure [CCN] + TX, ipsdienol (alternative name) [CCN] + TX, ipsenol (alternative name) [CCN] + TX, japonilure (alternative name) (481) + TX, lineatin (alternative name) [CCN] + TX, litlure (alternative name) [CCN] + TX, looplure (alternative name) [CCN] + TX, medlure [CCN] + TX, megatomoic acid (alternative name) [CCN] + TX, methyl eugenol (alternative name) (540) + TX, muscalure (563) + TX, octadeca-2,13-dien-l-yl acetate (IUPAC name) (588) + TX, octadeca-3,13-dien-l-yl acetate (IUPAC name) (589) + TX, orfralure (alternative name) [CCN] + TX, oryctalure (alternative name) (317) + TX, ostramone (alternative name) [CCN] + TX, siglure [CCN] + TX, sordidin (alternative name) (736) + TX, sulcatol (alternative name) [CCN] + TX, tetradec-ll-en-l-yl acetate (IUPAC name) (785) + TX, trimedlure (839) + TX, trimedlure A (alternative name) (839) + TX, trimedlure Bl (alternative name) (839) + TX, trimedlure B2 (alternative name) (839) + TX, trimedlure C (alternative name) (839) and trunc-call (alternative name) [CCN] + TX,
an insect repellent selected from the group of substances consisting of 2-(octylthio ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,
an insecticide selected from the group of substances consisting of 1-dichloro-l- nitroethane (IUPAC/Chemical Abstracts name) (1058) + TX, l,l-dichloro-2,2-bis(4- ethylphenyl)ethane (IUPAC name) (1056), + TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, l-bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916) + TX, 2,2,2- trichloro-l-(3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451) + TX, 2,2-dichlorovinyl 2- ethylsulphinylethyl methyl phosphate (IUPAC name) (1066) + TX, 2-(l,3-dithiolan-2- yl)phenyl dimethylcarbamate (IUPAC/ Chemical Abstracts name) (1109) + TX, 2-(2- butoxyethoxy)ethyl thiocyanate (IUPAC/Chemical Abstracts name) (935) + TX, 2-(4,5- dimethyl-l,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC/ Chemical Abstracts name) (1084) + TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name) (986) + TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984) + TX, 2-imidazolidone (IUPAC name) (1225) + TX, 2- isovalerylindan-l,3-dione (IUPAC name) (1246) + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate (IUPAC name) (1284) + TX, 2-thiocyanatoethyl laurate (IUPAC name) (1433) + TX, 3-bromo-l-chloroprop-l-ene (IUPAC name) (917) + TX, 3-methyl-l- phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283) + TX, 4-methyl(prop-2- ynyl)amino-3,5-xylyl methylcarbamate (IUPAC name) (1285) + TX, 5,5-dimethyl-3- oxocyclohex-l-enyl dimethylcarbamate (IUPAC name) (1085) + TX, abamectin (1) + TX, acephate (2) + TX, acetamiprid (4) + TX, acethion (alternative name) [CCN] + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, acrylonitrile (IUPAC name) (861) + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, aldrin (864) + TX, allethrin (17) + TX, allosamidin (alternative name) [CCN] + TX, allyxycarb (866) + TX, alpha- cypermethrin (202) + TX, alpha-ecdysone (alternative name) [CCN] + TX, aluminium phosphide (640) + TX, amidithion (870) + TX, amidothioate (872) + TX, aminocarb (873) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, anabasine (877) + TX, athidathion (883) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azadirachtin (alternative name) (41) + TX, azamethiphos (42) + TX, azinphos- ethyl (44) + TX, azinphos-methyl (45) + TX, azothoate (889) + TX, Bacillus thuringiensis delta endotoxins (alternative name) (52) + TX, barium hexafluorosilicate (alternative name) [CCN] + TX, barium polysulfide (IUPAC/Chemical Abstracts name) (892) + TX, barthrin
[CCN] + TX, Bayer 22/190 (development code) (893) + TX, Bayer 22408 (development code) (894) + TX, bendiocarb (58) + TX, benfuracarb (60) + TX, bensultap (66) + TX, beta- cyfluthrin (194) + TX, beta-cypermethrin (203) + TX, bifenthrin (76) + TX, bioallethrin (78) + TX, bioallethrin S-cyclopentenyl isomer (alternative name) (79) + TX, bioethanomethrin [CCN] + TX, biopermethrin (908) + TX, bioresmethrin (80) + TX, bis(2-chloroethyl) ether (IUPAC name) (909) + TX, bistrifluron (83) + TX, borax (86) + TX, brofenvalerate
(alternative name) + TX, bromfenvinfos (914) + TX, bromocyclen (918) + TX, bromo-DDT (alternative name) [CCN] + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX, bufencarb (924) + TX, buprofezin (99) + TX, butacarb (926) + TX, butathiofos (927) + TX, butocarboxim (103) + TX, butonate (932) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, calcium arsenate [CCN] + TX, calcium cyanide (444) + TX, calcium polysulfide (IUPAC name) (111) + TX, camphechlor (941) + TX, carbanolate (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbon disulfide (IUPAC/Chemical Abstracts name) (945) + TX, carbon tetrachloride (IUPAC name) (946) + TX, carbophenothion (947) + TX, carbosulfan (119) + TX, cartap (123) + TX, cartap hydrochloride (123) + TX, cevadine (alternative name) (725) + TX, chlorbicyclen (960) + TX, chlordane (128) + TX, chlordecone (963) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorethoxyfos (129) + TX, chlorfenapyr (130) + TX,
chlorfenvinphos (131) + TX, chlorfluazuron (132) + TX, chlormephos (136) + TX, chloroform [CCN] + TX, chloropicrin (141) + TX, chlorphoxim (989) + TX, chlorprazophos (990) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, chromafenozide (150) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, cis-resmethrin (alternative name) + TX, cismethrin (80) + TX, clocythrin (alternative name) + TX, cloethocarb (999) + TX, closantel (alternative name) [CCN] + TX, clothianidin (165) + TX, copper acetoarsenite [CCN] + TX, copper arsenate [CCN] + TX, copper oleate [CCN] + TX, coumaphos (174) + TX, coumithoate (1006) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos (1010) + TX, crufomate (1011) + TX, cryolite (alternative name) (177) + TX, CS 708 (development code) (1012) + TX, cyanofenphos (1019) + TX, cyanophos (184) + TX, cyanthoate (1020) + TX, cyclethrin [CCN] + TX, cycloprothrin (188) + TX, cyfluthrin (193) + TX, cyhalothrin (196) + TX, cypermethrin (201) + TX, cyphenothrin (206) + TX, cyromazine (209) + TX, cythioate (alternative name) [CCN] + TX, d-limonene (alternative name) [CCN] + TX, d-tetramethrin (alternative name) (788) + TX, DAEP (1031) + TX, dazomet (216) + TX, DDT (219) + TX, decarbofuran (1034) + TX, deltamethrin (223) + TX, demephion (1037) + TX, demephion-0 (1037) + TX, demephion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-0 (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-S-methyl (224) + TX, demeton-S- methylsulphon (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diamidafos (1044) + TX, diazinon (227) + TX, dicapthon (1050) + TX, dichlofenthion (1051) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicresyl (alternative name) [CCN] + TX, dicrotophos (243) + TX, dicyclanil (244) + TX, dieldrin (1070) + TX, diethyl 5- methylpyrazol-3-yl phosphate (IUPAC name) (1076) + TX, diflubenzuron (250) + TX, dilor (alternative name) [CCN] + TX, dimefluthrin [CCN] + TX, dimefox (1081) + TX, dimetan (1085) + TX, dimethoate (262) + TX, dimethrin (1083) + TX, dimethylvinphos (265) + TX, dimetilan (1086) + TX, dinex (1089) + TX, dinex-diclexine (1089) + TX, dinoprop (1093) + TX, dinosam (1094) + TX, dinoseb (1095) + TX, dinotefuran (271) + TX, diofenolan (1099) + TX, dioxabenzofos (1100) + TX, dioxacarb (1101) + TX, dioxathion (1102) + TX, disulfoton (278) + TX, dithicrofos (1108) + TX, DNOC (282) + TX, doramectin (alternative name) [CCN] + TX, DSP (1115) + TX, ecdysterone (alternative name) [CCN] + TX, EI 1642 (development code) (1118) + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, EMPC (1120) + TX, empenthrin (292) + TX, endosulfan (294) + TX, endothion (1121) + TX, endrin (1122) + TX, EPBP (1123) + TX, EPN (297) + TX, epofenonane (1124) + TX, eprinomectin (alternative name) [CCN] + TX, esfenvalerate (302) + TX, etaphos (alternative name) [CCN] + TX, ethiofencarb (308) + TX, ethion (309) + TX, ethiprole (310) + TX, ethoate-methyl (1134) + TX, ethoprophos (312) + TX, ethyl formate (IUPAC name) [CCN] + TX, ethyl-DDD (alternative name) (1056) + TX, ethylene dibromide (316) + TX, ethylene dichloride (chemical name) (1136) + TX, ethylene oxide [CCN] + TX, etofenprox (319) + TX, etrimfos (1142) + TX, EXD (1143) + TX, famphur (323) + TX, fenamiphos (326) + TX, fenazaflor (1147) + TX, fenchlorphos (1148) + TX, fenethacarb (1149) + TX, fenfluthrin (1150) + TX, fenitrothion (335) + TX, fenobucarb (336) + TX, fenoxacrim (1153) + TX, fenoxycarb (340) + TX, fenpirithrin (1155) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fensulfothion (1158) + TX, fenthion (346) + TX, fenthion-ethyl [CCN] + TX, fenvalerate (349) + TX, fipronil (354) + TX, flonicamid (358) + TX,
flubendiamide (CAS. Reg. No.: 272451-65-7) + TX, flucofuron (1168) + TX, flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1169) + TX, flufenerim [CCN] + TX, flufenoxuron (370) + TX, flufenprox (1171) + TX, flumethrin (372) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, fonofos (1191) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1192) + TX, formparanate (1193) + TX, fosmethilan (1194) + TX, fospirate (1195) + TX, fosthiazate (408) + TX, fosthietan (1196) + TX, furathiocarb (412) + TX, furethrin (1200) + TX, gamma-cyhalothrin (197) + TX, gamma-HCH (430) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, GY-81 (development code) (423) + TX, halfenprox (424) + TX, halofenozide (425) + TX, HCH (430) + TX, HEOD (1070) + TX, heptachlor (1211) + TX, heptenophos (432) + TX, heterophos [CCN] + TX, hexaflumuron (439) + TX, HHDN (864) + TX, hydramethylnon (443) + TX, hydrogen cyanide (444) + TX, hydroprene (445) + TX, hyquincarb (1223) + TX, imidacloprid (458) + TX, imiprothrin (460) + TX, indoxacarb (465) + TX, iodomethane (IUPAC name) (542) + TX, IPSP (1229) + TX, isazofos (1231) + TX, isobenzan (1232) + TX, isocarbophos (alternative name) (473) + TX, isodrin (1235) + TX, isofenphos (1236) + TX, isolane (1237) + TX, isoprocarb (472) + TX, isopropyl 0-(methoxy- aminothiophosphoryl)salicylate (IUPAC name) (473) + TX, isoprothiolane (474) + TX, isothioate (1244) + TX, isoxathion (480) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, juvenile hormone I (alternative name) [CCN] + TX, juvenile hormone II (alternative name) [CCN] + TX, juvenile hormone III (alternative name) [CCN] + TX, kelevan (1249) + TX, kinoprene (484) + TX, lambda-cyhalothrin (198) + TX, lead arsenate [CCN] + TX, lepimectin (CCN) + TX, leptophos (1250) + TX, lindane (430) + TX, lirimfos (1251) + TX, lufenuron (490) + TX, lythidathion (1253) + TX, m-cumenyl methylcarbamate (IUPAC name) (1014) + TX, magnesium phosphide (IUPAC name) (640) + TX, malathion (492) + TX, malonoben (1254) + TX, mazidox (1255) + TX, mecarbam (502) + TX, mecarphon (1258) + TX, menazon (1260) + TX, mephosfolan (1261) + TX, mercurous chloride (513) + TX, mesulfenfos (1263) + TX, metaflumizone (CCN) + TX, metam (519) + TX, m eta m- potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methanesulphonyl fluoride (IUPAC/Chemical Abstracts name) (1268) + TX, methidathion (529) + TX, methiocarb (530) + TX, methocrotophos (1273) + TX, methomyl (531) + TX, methoprene (532) + TX, methoquin-butyl (1276) + TX, methothrin (alternative name) (533) + TX, methoxychlor (534) + TX, methoxyfenozide (535) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, methylchloroform (alternative name) [CCN] + TX, methylene chloride [CCN] + TX, metofluthrin [CCN] + TX, metolcarb (550) + TX,
metoxadiazone (1288) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, mirex (1294) + TX, monocrotophos (561) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naftalofos (alternative name) [CCN] + TX, naled (567) + TX,
naphthalene (IUPAC/Chemical Abstracts name) (1303) + TX, NC-170 (development code) (1306) + TX, NC-184 (compound code) + TX, nicotine (578) + TX, nicotine sulfate (578) + TX, nifluridide (1309) + TX, nitenpyram (579) + TX, nithiazine (1311) + TX, nitrilacarb (1313) + TX, nitrilacarb 1: 1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, nornicotine (traditional name) (1319) + TX, novaluron (585) + TX, noviflumuron (586) + TX, 0-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate (IUPAC name) (1057) + TX, 0,0-diethyl 0-4-methyl-2-oxo-2H- chromen-7-yl phosphorothioate (IUPAC name) (1074) + TX, Ο,Ο-diethyl 0-6-methyl-2- propylpyrimidin-4-yl phosphorothioate (IUPAC name) (1075) + TX, Ο,Ο,Ο',Ο'-tetrapropyl dithiopyrophosphate (IUPAC name) (1424) + TX, oleic acid (IUPAC name) (593) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydemeton-methyl (609) + TX, oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, para-dichlorobenzene [CCN] + TX, parathion (615) + TX, parathion-methyl (616) + TX, penfluron (alternative name) [CCN] + TX, pentachlorophenol (623) + TX, pentachlorophenyl laurate (IUPAC name) (623) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, PH 60-38 (development code) (1328) + TX, phenkapton (1330) + TX, phenothrin (630) + TX, phenthoate (631) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosnichlor (1339) + TX, phosphamidon (639) + TX, phosphine (IUPAC name) (640) + TX, phoxim (642) + TX, phoxim-methyl (1340) + TX, pirimetaphos (1344) + TX, pirimicarb (651) + TX, pirimiphos-ethyl (1345) + TX, pirimiphos-methyl (652) + TX, polychlorodicyclopentadiene isomers (IUPAC name) (1346) + TX, polychloroterpenes (traditional name) (1347) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate
[CCN] + TX, prallethrin (655) + TX, precocene I (alternative name) [CCN] + TX, precocene II (alternative name) [CCN] + TX, precocene III (alternative name) [CCN] + TX, primidophos (1349) + TX, profenofos (662) + TX, profluthrin [CCN] + TX, promacyl (1354) + TX, promecarb (1355) + TX, propaphos (1356) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothiofos (686) + TX, prothoate (1362) + TX,
protrifenbute [CCN] + TX, pymetrozine (688) + TX, pyraclofos (689) + TX, pyrazophos (693) + TX, pyresmethrin (1367) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridalyl (700) + TX, pyridaphenthion (701) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, pyriproxyfen (708) + TX, quassia
(alternative name) [CCN] + TX, quinalphos (711) + TX, quinalphos-methyl (1376) + TX, quinothion (1380) + TX, quintiofos (1381) + TX, R-1492 (development code) (1382) + TX, rafoxanide (alternative name) [CCN] + TX, resmethrin (719) + TX, rotenone (722) + TX, RU 15525 (development code) (723) + TX, RU 25475 (development code) (1386) + TX, ryania (alternative name) (1387) + TX, ryanodine (traditional name) (1387) + TX, sabadilla
(alternative name) (725) + TX, schradan (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, SI-0205 (compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, silafluofen (728) + TX, SN 72129 (development code) (1397) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoride (IUPAC/Chemical Abstracts name) (1399) + TX, sodium hexafluorosilicate (1400) + TX, sodium pentachlorophenoxide (623) + TX, sodium selenate (IUPAC name) (1401) + TX, sodium thiocyanate [CCN] + TX, sophamide (1402) + TX, spinosad (737) + TX, spiromesifen (739) + TX, spirotetrmat (CCN) + TX, sulcofuron (746) + TX, sulcofuron-sodium (746) + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulphuryl fluoride (756) + TX, sulprofos (1408) + TX, tar oils (alternative name) (758) + TX, tau-fluvalinate (398) + TX, tazimcarb (1412) + TX, TDE (1414) + TX, tebufenozide (762) + TX, tebufenpyrad (763) + TX, tebupirimfos (764) + TX, teflubenzuron (768) + TX, tefluthrin (769) + TX, temephos (770) + TX, TEPP (1417) + TX, terallethrin (1418) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachloroethane [CCN] + TX, tetrachlorvinphos (777) + TX, tetramethrin (787) + TX, theta-cypermethrin (204) + TX, thiacloprid (791) + TX, thiafenox (alternative name) + TX, thiamethoxam (792) + TX, thicrofos (1428) + TX, thiocarboxime (1431) + TX, thiocyclam (798) + TX, thiocyclam hydrogen oxalate (798) + TX, thiodicarb (799) + TX, thiofanox (800) + TX, thiometon (801) + TX, thionazin (1434) + TX, thiosultap (803) + TX, thiosultap-sodium (803) + TX, thuringiensin (alternative name) [CCN] + TX, tolfenpyrad (809) + TX, tralomethrin (812) + TX, transfluthrin (813) + TX, transpermethrin (1440) + TX, triamiphos (1441) + TX, triazamate (818) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, trichlormetaphos-3 (alternative name) [CCN] + TX, trichloronat (1452) + TX, trifenofos (1455) + TX, triflumuron (835) + TX, trimethacarb (840) + TX, triprene (1459) + TX, vamidothion (847) + TX, vaniliprole [CCN] + TX, veratridine (alternative name) (725) + TX, veratrine (alternative name) (725) + TX, XMC (853) + TX, xylylcarb (854) + TX, YI-5302 (compound code) + TX, zeta-cypermethrin (205) + TX, zetamethrin (alternative name) + TX, zinc phosphide (640) + TX, zolaprofos (1469) and ZXI 8901 (development code) (858) + TX, cyantraniliprole [736994-63-19] + TX, chlorantraniliprole [500008-45-7] + TX, cyenopyrafen [560121-52-0] + TX, cyflumetofen [400882-07-7] + TX, pyrifluquinazon
[337458-27-2] + TX, spinetoram [187166-40-1 + 187166-15-0] + TX, spirotetramat
[203313-25-1] + TX, sulfoxaflor [946578-00-3] + TX, flufiprole [704886-18-0] + TX, meperfluthrin [915288-13-0] + TX, tetramethylfluthrin [84937-88-2] + TX,
a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (IUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, trifenmorph (1454) + TX, trimethacarb (840) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, pyriprole [394730-71-3] + TX,
a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, l,2-dibromo-3-chloropropane (IUPAC/Chemical Abstracts name) (1045) + TX, 1,2-dichloropropane (IUPAC/ Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4- dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/Chemical Abstracts name) (1065) + TX, 3- (4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-l,3,5- thiadiazinan-3-ylacetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine
(alternative name) (210) + TX, abamectin (1) + TX, acetoprole [CCN] + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, AZ 60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbosulfan (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, cloethocarb (999) + TX, cytokinins (alternative name) (210) + TX, dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidafos (1044) + TX, dichlofenthion (1051) + TX, dicliphos (alternative name) + TX, dimethoate (262) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ethoprophos (312) + TX, ethylene dibromide (316) + TX, fenamiphos (326) + TX, fenpyrad (alternative name) + TX, fensulfothion (1158) + TX, fosthiazate (408) + TX, fosthietan (1196) + TX, furfural (alternative name) [CCN] + TX, GY-81 (development code) (423) + TX, heterophos [CCN] + TX, iodomethane (IUPAC name) (542) + TX, isamidofos (1230) + TX, isazofos (1231) + TX, ivermectin (alternative name) [CCN] + TX, kinetin (alternative name) (210) + TX, mecarphon (1258) + TX, metam (519) + TX, m eta m- potassium
(alternative name) (519) + TX, metam-sodium (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, Myrothecium verrucaria composition (alternative name) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidon (639) + TX, phosphocarb [CCN] + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrach roth iophene (IUPAC/ Chemical Abstracts name) (1422) + TX, thiafenox (alternative name) + TX, thionazin (1434) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, xylenols [CCN] + TX, YI-5302 (compound code) and zeatin (alternative name) (210) + TX, fluensulfone [318290-98-1] + TX,
a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX,
a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX,
a rodenticide selected from the group of substances consisting of 2-isovalerylindan-l,3- dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91) + TX, bromethalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorophacinone (140) + TX, cholecalciferol (alternative name) (850) + TX, coumachlor (1004) + TX, coumafuryl (1005) + TX, coumatetralyl (175) + TX, crimidine (1009) + TX, difenacoum (246) + TX, difethialone (249) + TX, diphacinone (273) + TX, ergocalciferol (301) + TX, flocoumafen (357) + TX, fluoroacetamide (379) + TX, flupropadine (1183) + TX, flupropadine hydrochloride (1183) + TX, gamma-HCH (430) + TX, HCH (430) + TX, hydrogen cyanide (444) + TX, iodomethane (IUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (IUPAC name) (640) + TX, methyl bromide (537) + TX, norbormide (1318) + TX, phosacetim (1336) + TX, phosphine (IUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone (1341) + TX, potassium arsenite [CCN] + TX, pyrinuron (1371) + TX, scilliroside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851) and zinc phosphide (640) + TX,
a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934) + TX, 5-(l,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX, an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, thiram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX,
a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN] + TX,
a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX,
and biologically active compounds selected from the group consisting of azaconazole (60207-31-0] + TX, bitertanol [70585-36-3] + TX, bromuconazole [116255-48-2] + TX, cyproconazole [94361-06-5] + TX, difenoconazole [119446-68-3] + TX, diniconazole [83657- 24-3] + TX, epoxiconazole [106325-08-0] + TX, fenbuconazole [114369-43-6] + TX, fluquinconazole [136426-54-5] + TX, flusilazole [85509-19-9] + TX, flutriafol [76674-21-0] + TX, hexaconazole [79983-71-4] + TX, imazalil [35554-44-0] + TX, imibenconazole [86598- 92-7] + TX, ipconazole [125225-28-7] + TX, metconazole [125116-23-6] + TX, myclobutanil [88671-89-0] + TX, pefurazoate [101903-30-4] + TX, penconazole [66246-88-6] + TX, prothioconazole [178928-70-6] + TX, pyrifenox [88283-41-4] + TX, prochloraz [67747-09-5] + TX, propiconazole [60207-90-1] + TX, simeconazole [149508-90-7] + TX, tebuconazole [107534-96-3] + TX, tetraconazole [112281-77-3] + TX, triadimefon [43121-43-3] + TX, triadimenol [55219-65-3] + TX, triflumizole [99387-89-0] + TX, triticonazole [131983-72-7] + TX, ancymidol [12771-68-5] + TX, fenarimol [60168-88-9] + TX, nuarimol [63284-71-9] + TX, bupirimate [41483-43-6] + TX, dimethirimol [5221-53-4] + TX, ethirimol [23947-60-6] + TX, dodemorph [1593-77-7] + TX, fenpropidine [67306-00-7] + TX, fenpropimorph [67564- 91-4] + TX, spiroxamine [118134-30-8] + TX, tridemorph [81412-43-3] + TX, cyprodinil 5 [121552-61-2] + TX, mepanipyrim [110235-47-7] + TX, pyrimethanil [53112-28-0] + TX, fenpiclonil [74738-17-3] + TX, fludioxonil [131341-86-1] + TX, benalaxyl [71626-11-4] + TX, furalaxyl [57646-30-7] + TX, metalaxyl [57837-19-1] + TX, R-metalaxyl [70630-17-0] + TX, ofurace [58810-48-3] + TX, oxadixyl [77732-09-3] + TX, benomyl [17804-35-2] + TX, carbendazim [10605-21-7] + TX, debacarb [62732-91-6] + TX, fuberidazole [3878-19-1] +
10 TX, thiabendazole [148-79-8] + TX, chlozolinate [84332-86-5] + TX, dichlozoline [24201-58- 9] + TX, iprodione [36734-19-7] + TX, myclozoline [54864-61-8] + TX, procymidone
[32809-16-8] + TX, vinclozoline [50471-44-8] + TX, boscalid [188425-85-6] + TX, carboxin [5234-68-4] + TX, fenfuram [24691-80-3] + TX, flutolanil [66332-96-5] + TX, mepronil [55814-41-0] + TX, oxycarboxin [5259-88-1] + TX, penthiopyrad [183675-82-3] + TX,
15 thifluzamide [130000-40-7] + TX, guazatine [108173-90-6] + TX, dodine [2439-10-3] [112- 65-2] (free base) + TX, iminoctadine [13516-27-3] + TX, azoxystrobin [131860-33-8] + TX, dimoxystrobin [149961-52-4] + TX, enestroburin {Proc. BCPC, Int. Congr., Glasgow, 2003, 1, 93} + TX, fluoxastrobin [361377-29-9] + TX, kresoxim-methyl [143390-89-0] + TX, metominostrobin [133408-50-1] + TX, trifloxystrobin [141517-21-7] + TX, orysastrobin
20 [248593-16-0] + TX, picoxystrobin [117428-22-5] + TX, pyraclostrobin [175013-18-0] + TX, ferbam [14484-64-1] + TX, mancozeb [8018-01-7] + TX, maneb [12427-38-2] + TX, metiram [9006-42-2] + TX, propineb [12071-83-9] + TX, thiram [137-26-8] + TX, zineb [12122-67-7] + TX, ziram [137-30-4] + TX, captafol [2425-06-1] + TX, captan [133-06-2] + TX, dichlofluanid [1085-98-9] + TX, fluoroimide [41205-21-4] + TX, folpet [133-07-3 ] + TX,
25 tolylfluanid [731-27-1] + TX, bordeaux mixture [8011-63-0] + TX, copperhydroxid [20427- 59-2] + TX, copperoxychlorid [1332-40-7] + TX, coppersulfat [7758-98-7] + TX, copperoxid [1317-39-1] + TX, mancopper [53988-93-5] + TX, oxine-copper [10380-28-6] + TX, dinocap [131-72-6] + TX, nitrothal-isopropyl [10552-74-6] + TX, edifenphos [17109-49-8] + TX, iprobenphos [26087-47-8] + TX, isoprothiolane [50512-35-1] + TX, phosdiphen [36519-00-
30 3] + TX, pyrazophos [13457-18-6] + TX, tolclofos-methyl [57018-04-9] + TX, acibenzolar-S- methyl [135158-54-2] + TX, anilazine [101-05-3] + TX, benthiavalicarb [413615-35-7] + TX, blasticidin-S [2079-00-7] + TX, chinomethionat [2439-01-2] + TX, chloroneb [2675-77-6] + TX, chlorothalonil [1897-45-6] + TX, cyflufenamid [180409-60-3] + TX, cymoxanil [57966- 95-7] + TX, dichlone [117-80-6] + TX, diclocymet [139920-32-4] + TX, diclomezine [62865-
35 36-5] + TX, dicloran [99-30-9] + TX, diethofencarb [87130-20-9] + TX, dimethomorph
[110488-70-5] + TX, SYP-LI90 (Flumorph) [211867-47-9] + TX, dithianon [3347-22-6] + TX, ethaboxam [162650-77-3] + TX, etridiazole [2593-15-9] + TX, famoxadone [131807-57-3] + TX, fenamidone [161326-34-7] + TX, fenoxanil [115852-48-7] + TX, fentin [668-34-8] + TX, ferimzone [89269-64-7] + TX, fluazinam [79622-59-6] + TX, fluopicolide [239110-15-7] + TX, flusulfamide [106917-52-6] + TX, fenhexamid [126833-17-8] + TX, fosetyl-aluminium [39148-24-8] + TX, hymexazol [10004-44-1] + TX, iprovalicarb [140923-17-7] + TX, IKF-916 (Cyazofamid) [120116-88-3] + TX, kasugamycin [6980-18-3] + TX, methasulfocarb [66952-49-6] + TX, metrafenone [220899-03-6] + TX, pencycuron [66063-05-6] + TX, phthalide [27355-22-2] + TX, polyoxins [11113-80-7] + TX, probenazole [27605-76-1] + TX, propamocarb [25606-41-1] + TX, proquinazid [189278-12-4] + TX, pyroquilon [57369-32-1] + TX, quinoxyfen [124495-18-7] + TX, quintozene [82-68-8] + TX, sulphur [7704-34-9] + TX, tiadinil [223580-51-6] + TX, triazoxide [72459-58-6] + TX, tricyclazole [41814-78-2] + TX, triforine [26644-46-2] + TX, validamycin [37248-47-8] + TX, zoxamide (RH7281)
[156052-68-5] + TX, mandipropamid [374726-62-2] + TX, isopyrazam [881685-58-1] + TX, sedaxane [874967-67-6] + TX, 3-difluoromethyl-l-methyl-lH-pyrazole-4-carboxylic acid (9- dichloromethylene-l,2,3,4-tetrahydro-l,4-methano-naphthalen-5-yl)-amide (dislosed in WO 2007/048556) + TX, 3-difluoromethyl-l-methyl-lH-pyrazole-4-carboxylic acid [2-(2,4- dichlorophenyl)-2-methoxy-l-methyl-ethyl]-amide (disclosed in WO 2008/148570) + TX, 1- [4-[4-[(5S)5-(2,6-difluorophenyl)-4,5-dihydro-l,2-oxazol-3-yl]-l,3-thiazol-2-yl]piperidin-l-yl]- 2-[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]ethanone + TX, l-[4-[4-[5-(2,6- difluorophenyl)-4,5-dihydro-l,2-oxazol-3-yl]-l,3-thiazol-2-yl]piperidin-l-yl]-2-[5-methyl-3- (trifluoromethyl)-lH-pyrazol-l-yl]ethanone [1003318-67-9], both disclosed in WO
2010/123791, WO 2008/013925, WO 2008/013622 and WO 2011/051243 page 20) +TX, and 3-difluoromethyl-l-methyl-lH-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)- amide (dislosed in WO 2006/087343) + TX.
Throughout this document the expression "composition" stands for the various mixtures or combinations of components TX and (B), for example in a single "ready-mix" form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the components TX and (B) is not essential for working the present invention.
The compositions according to the invention may also comprise more than one of the active components (B), if, for example, a broadening of the spectrum of disease control is desired. For instance, it may be advantageous in the agricultural practice to combine two or three components (B) with component TX. An example is a composition comprising a compound of formula (I), azoxystrobin and cyproconazole. In the above different lists of active ingredients to be mixed with a TX, the compound of the formula I is preferably a compound of Tables 1-34 and Tables 38-39, and more preferably, a compound selected from P.01, P.02, P.03, P.04, P.05, P.08, P.09, P.10, P.11, P.12, P.13, P.14, P.15, P.16, P.17, P.18, P.19, P.20, P.21, P.22, P.23A, P.24, P.29, P.33, P.34, P. 35, P.37, P.38, P.39, P.45, P.46, P.47, P.49, P.50, P.51, P.53, P.54, P.55, P.56, P.57, P.58, P.60, P.61, P.62, P.63A, P.64, P.65, P.66, P.67, P.68, P.69, P.71, P.72, P.74, P.75, P.76, P.77, P.78, P.79, P.80, P.82, P.83, P.84, P.85, P.86, P.87, P.88, P.89, P.90, P.91, P.92, P.94, P.95, P.96, P.97, P.98, P.99, P.100, P.102, P.103, P.101, P.104, P.105, P.107, P.108.
In the above-mentioned mixtures of compounds of formula I, in particular a compound selected from said Tables 1-34 and Tables 38-39, with other insecticides, fungicides, herbicides, safeners, adjuvants and the like, the mixing ratios can vary over a large range and are, preferably 100: 1 to 1:6000, especially 50: 1 to 1:50, more especially 20: 1 to 1:20, even more especially 10: 1 to 1: 10. Those mixing ratios are understood to include, on the one hand, ratios by weight and also, on other hand, molar ratios.
The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of TX with the mixing partner).
Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type. In these circumstances other formulation types may be prepared. For example, where one active ingredient is a water insoluble solid and the other a water insoluble liquid, it may nevertheless be possible to disperse each active ingredient in the same continuous aqueous phase by dispersing the solid active ingredient as a suspension (using a preparation analogous to that of an SC) but dispersing the liquid active ingredient as an emulsion (using a preparation analogous to that of an EW). The resultant composition is a suspoemulsion (SE) formulation.
It has been found, surprisingly, that certain weight ratios of component TX to component (B) are able to give rise to synergistic activity. Therefore, a further aspect of the invention are compositions, wherein component TX and component (B) are present in the composition in amounts producing a synergistic effect. This synergistic activity is apparent from the fact that the fungicidal activity of the composition comprising component TX and component (B) is greater than the sum of the fungicidal activities of component TX and of component (B). This synergistic activity extends the range of action of component TX and component (B) in two ways. Firstly, the rates of application of component TX and component (B) are lowered whilst the action remains equally good, meaning that the active ingredient mixture still achieves a high degree of phytopathogen control even where the two individual components have become totally ineffective in such a low application rate range. Secondly, there is a substantial broadening of the spectrum of phytopathogens that can be controlled.
A synergistic effect exists whenever the action of an active ingredient combination is greater than the sum of the actions of the individual components. The action to be expected E for a given active ingredient combination obeys the so-called COLBY formula and can be calculated as follows (COLBY, S.R. "Calculating synergistic and antagonistic responses of herbicide combination". Weeds, Vol. 15, pages 20-22; 1967):
ppm = milligrams of active ingredient (= a.i.) per liter of spray mixture
X = % action by active ingredient A) using p ppm of active ingredient
Y = % action by active ingredient B) using q ppm of active ingredient.
According to COLBY, the expected (additive) action of active ingredients A)+B) using p+q ppm of active ingredient is 1 uu
If the action actually observed (O) is greater than the expected action (E), then the action of the combination is super-additive, i.e. there is a synergistic effect. In mathematical terms, synergism corresponds to a positive value for the difference of (O-E). In the case of purely complementary addition of activities (expected activity), said difference (O-E) is zero. A negative value of said difference (O-E) signals a loss of activity compared to the expected activity.
However, besides the actual synergistic action with respect to fungicidal activity, the compositions according to the invention can also have further surprising advantageous properties. Examples of such advantageous properties that may be mentioned are: more advantageuos degradability; improved toxicological and/or ecotoxicological behaviour; or improved characteristics of the useful plants including: emergence, crop yields, more developed root system, tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf colour, less fertilizers needed, less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, improved plant vigor, and early germination.
Some compositions according to the invention have a systemic action and can be used as foliar, soil and seed treatment fungicides.
With the compositions according to the invention it is possible to inhibit or destroy the phytopathogenic microorganisms which occur in plants or in parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different useful plants, while at the same time the parts of plants which grow later are also protected from attack by phytopathogenic microorganisms. The compositions according to the invention can be applied to the phytopathogenic microorganisms, the useful plants, the locus thereof, the propagation material thereof, storage goods or technical materials threatened by microorganism attack.
The compositions according to the invention may be applied before or after infection of the useful plants, the propagation material thereof, storage goods or technical materials by the microorganisms.
A further aspect of the present invention is a method of controlling diseases on useful plants or on propagation material thereof caused by phytopathogens, which comprises applying to the useful plants, the locus thereof or propagation material thereof a composition according to the invention. Preferred is a method, which comprises applying to the useful plants or to the locus thereof a composition according to the invention, more preferably to the useful plants. Further preferred is a method, which comprises applying to the
propagation material of the useful plants a composition according to the invention.
The compositions according to the invention may also comprise more than one of the active components (B), if, for example, a broadening of the spectrum of disease control is desired. For instance, it may be advantageous in the agricultural practice to combine two or three components (B) with component TX. An example is a composition comprising a compound of formula (I), azoxystrobin and cyproconazole. The following non-limiting Examples illustrate the above-described invention in greater detail without limiting it. Those skilled in the art will promptly recognise appropriate variations from the procedures both as to reactants and as to reaction conditions and techniques. All references mentioned herein are incorporated by reference in their entirety. Preparatory examples:
Throughout these examples, the isomer drawn is in excess in the reaction mixture and/or product
Example 1: Preparation of compound P.12
Figure imgf000138_0001
(E)-l-(6-{3-[l-(6-Methyl-pyridin-2-yl)-eth-(E)-ylideneaminooxy]-prop-l-ynyl}-pyridin-2- yl)-ethanone O-methyl-oxime (85mg) was dissolved in ethanol (lOmL). Palladium on carbon (5% on charcoal; 5mg) was added and the reaction mixture was stirred for 16h under an atmosphere of hydrogen. The reaction mixture was filtered, evaporated and purified over silica to give a yellow oil (13mg). 1H-NMR (CDCI3, 400 MHz):7.70 (d, 1H), 7.68 (d, 1H), 7.69-7.50 (m, 2H), 7.12 (d, 1H), 7.10 (d, 1H), 4.39 (t, 2H), 4.01 (s, 3H), 2.92 (t, 2H), 2.32 (s, 6H), 2.21 (m, 2H)
Preparation of rEVl-r6-{3-ri-r6-methyl-pyndin-2-yn-etri-rEVylideneaminooxy1-prop-l- ynyl}- ridin-2-y0-ethanone O-methyl-oxime
Figure imgf000139_0001
Sodium hydride (55% w/w in mineral oil; 22mg) was added at 0-5°C to a solution of (E)-l-(6-methyl-pyridin-2-yl)-ethanone oxime (50mg) in dimethylformamide (3.5ml_). After stirring for 20min at 0-5°C a solution of methanesulfonic acid 3-(6-{l-[(E)-methoxyimino]- ethyl}-pyridin-2-yl)-prop-2-ynyl ester (94mg) in dimethylformamide (0.5ml_) was added. The reaction mixture was the stirred for 3h at ambient temperature, then diluted with ethyl acetate and washed with water. The organic phase was separated, dried over sodium sulphate and concentrated to give brown material (85mg) which was used without further purification in the next step.
Preparation of methanesulfonic acid 3-r6- i-rrE>methoxyimino1-ethyl>-pyridin-2-yn- prop-2- nyl ester
Figure imgf000139_0002
Methane sulfonyl chloride (118mg) was added at 0-5°C to a solution of triethylamine (0.21ml_) and (E)-l-[6-(3-hydroxy-prop-l-ynyl)-pyridin-2-yl]-ethanone O-methyl-oxime (150mg) in dichloromethane (3.0ml_). After stirring for lOmin at 5°C and 90min at ambient temperature sodium bicarbonate (10% w/w aqueous solution; lmL) was added and the reaction mixture was diluted with dichloromethane, washed with water and brine and dried over sodium sulfate. Filtration and concentration gave a yellow residue (211mg) which was used directly in the next step. Pre aration of fEM-r6-f3-hydroxy-prop-l-ynyl>pyridin-2-yn-ethanone O-methyl-oxime
Figure imgf000140_0001
Sodium-acetate (490mg) and O-methyl-hydroxylamine hydrochloride (396mg) were added to a solution of l-[6-(3-hydroxy-prop-l-ynyl)-pyridin-2-yl]-ethanone (700mg) in methanol (7ml_). After stirring for 16h at ambient temperature the reaction mixture was diluted with ethyl acetate, washed with water and dried over sodium sulphate. Filtration and concentration gave a beige solid (729mg). ^-NMR (CDCI3, 400 MHz):7.99 (d, 1H), 7.64 (t, 1H), 7.49 (d, 1H), 4.53 (s, 2H), 4.3 (s, 3H), 2.31 (s, 3H), 1.88 (s broad, 1H) Pre aration of l-r6-f3-hydroxy-prop-l-ynylVpyridin-2-yn-ethanone
Figure imgf000140_0002
2-Acetyl-6-bromopyridine (lOg) and propargyl alcohol (3.64g) were dissolved in THF (150ml_). Diisopropylamine (14.1ml_), dichlorobis (triphenylphospine) palladium(II) (1.4g) and copper(I) iodide (0.99g) were added. After stirring for 16h at 70°C the reaction mixture was concentrated to 1/3 of the volume, diluted with ethyl acetate, washed with sodium bicarbonate (10% w/w aqueous solution) and brine. The organic phase was dried over sodium sulphate, concentrated and purified by chromatography over silica to give a beige solid (6.8g). ^-NMR (CDCI3, 400 MHz):7.99 (d, 1H), 7.80 (t, 1H), 7.60 (d, 1H), 4.60 (d, 2H), 2.74 (d, 3H), 2.26 (t, 1H)
Example 2: Preparation of compound P.09
Figure imgf000140_0003
Sodium acetate (lOmg) and O-allyl-hydroxylamine hydrochloride (13mg) were added to a solution of l-(6-{3-[l-(6-methyl-pyridin-2-yl)-eth-(E)-ylideneaminooxy]-propyl}-pyridin-2- yl)-ethanone (30mg) in methanol (4ml_) After stirring for 16h at ambient temperature the reaction mixture was diluted with ethyl acetate, washed with water and dried over sodium sulphate. Filtration and concentration gave 31mg of light yellow oil. 1H-NMR (CDCI3, 400 MHz): 7.70 (d, 1H), 7.68 (d, 1H), 7.58-7.50 (m, 2H), 7.12-7.05 (m, 2H), 6.12-6.02 (m, 1H), 5.49-5.20 (m, 2H) 4.72 (d, 2H), 4.39 (t, 2H), 2.92 (t, 2H), 2.57 (s, 3H), 2.37 (s, 3H), 2.32 (s, 3H), 2.22 (m, 2H)
Preparation of l-r6-{3-ri-r6-methyl-pyndin-2-yl>eth-rEVylideneaminooxy1-propyl>- pyridin-2- O-ethanone
Figure imgf000141_0001
l-(6-{3-[l-(6-Methyl-pyridin-2-yl)-eth-(E)-ylideneaminooxy]-prop-l-ynyl}-pyridin-2-yl)- ethanone (290mg) was dissolved in ethanol (lOmL). Palladium (5% on charcoal; 20mg) was added and the reaction mixture was stirred for 16h under an atmosphere of hydrogen. The reaction mixture was filtered, evaporated and purified over silica to give a yellow oil
(239mg). ^-NMR (CDCI3, 400 MHz):7.85 (d, 1H), 7.72 (t, 1H), 7.68 (d, 1H), 7.53 (t, 1H), 7.33 (d, 1H), 7.10 (d, 1H), 4.31 (t, 2H), 3.00 (t, 2H), 2.71 (s, 3H), 2.56 (s, 3H), 2.31 (s, 3H), 2.25 (m, 2H)
Preparation of l-(,6- 3-ri-(,6-methyl-pyridin-2-vn-eth-(E>ylideneaminooxy1-prop-l-vnyl>- pyridin-2-vO-ethanone
Figure imgf000141_0002
2-Acetyl-6-bromopyridine (500mg) and (E)-l-(6-methyl-pyridin-2-yl)-ethanone O-prop- 2-ynyl-oxime (470mg) were dissolved in THF (lOmL). Diisopropylamine (0.72ml_), dichlorobis (triphenylphospine) palladium (II) (53mg) and copper (I) iodide (38mg) were added. After stirring for 16h at 70°C the reaction mixture was diluted with ethyl acetate, washed with sodium bicarbonate (10% w/w aqueous solution) and brine. The organic phase was dried over sodium sulphate, concentrated and purified by chromatography over silica to give a beige solid (430mg). ^-NMR (CDCI3, 400 MHz):7.98 (d, 1H), 7.79 (t, 1H), 7.73 (d, 1H), 7.63 (d, 1H), 7.58 (t, 1H), 7.12 (d, 1H), 5.10 (s, 2H), 2.73 (s, 3H), 2.48 (s, 3H), 2.40 (s, 3H) Preparation of fEM-f6-methyl-pyridin-2-yO-ethanone O-prop-2-ynyl-oxime
Figure imgf000142_0001
2-Acetyl-6-methyl-pyridine (1.5g) was dissolved in ethanol (lOmL). Sodium acetate (1.37g) and O-propargyl-hydroxylamine hydrochloride (1.45g) were added. After stirring for 16h at ambient temperature the reaction mixture was diluted with ethyl acetate, washed with water, dried over sodium sulphate, filtrated and evaporated to give a brown oil (1.9g). ^-NMR (CDCI3, 400 MHz):7.70 (d, 1H), 7.54 (t, 1H), 7.10 (d, 1H), 4.81 (s, 2H), 2.58 (s, 3H), 2.49 (s, 1H), 2.37 (s, 3H) Example 3: Preparation of compound P.03
Figure imgf000142_0002
Sodium acetate (lOmg) and O-methyl-hydroxylamine hydrochloride (8mg) were added to a solution of l-(6-{2-methyl-3-[l-(6-methyl-pyridin-2-yl)-eth-(E)-ylideneaminooxy] propyl}-pyridin-2-yl)-ethanone (25mg) in methanol (5ml_). After stirring for 16h at ambient temperature the reaction mixture was diluted with ethyl acetate, washed with water and dried over sodium sulphate. Filtration and concentration gave a light yellow oil (27mg). ^ NMR (CDCI3, 400 MHz):7.63 (d, 1H), 7.59 (d, 1H), 7.50-7.41 (m, 2H), 7.05-6.97 (2d, 2H), 4.13-4.00 (m, 2H), 3.94 (s, 3H), 2.90 (dd, 1H), 2.60 (dd, 1H), 2.50 (m, 4H), 2.74 (2s, 6H), 0.92 (d, 3H).
Preparation of l-r6- 2-methyl-3-ri-r6-methyl-pyridin-2-yn-eth-rEVylideneaminooxy1- prop l}-pyridin-2-y0-ethanone
Figure imgf000142_0003
l,l,l-Tris(acetyloxy)-l,l-dihydro-l,2-benziodoxol-3-(lH)-one (55mg) was added to a solution of (E)-l-(6-methyl-pyridin-2-yl)-ethanone 0-{3-[6-(l-hydroxy-ethyl)-pyridin-2-yl]-2- methyl-propyl}-oxime (34mg) in dichloromethane (3ml_). After stirring for 16h at ambient temperature, sodium hydrogen carbonate (2ml_; 20% aqueous solution) and sodium thiosulphate (2ml_; 30% aqueous solution) were added. After stirring for further 40min the organic phase was separated, washed with water, dried over sodium sulphate, filtered and purified by chromatography over silica to give a colorless oil (25mg) ^-NMR (CDCI3, 400 MHz): 7.85 (d, IH), 7.70 (t, IH), 7.65 (d, IH), 7.54 (t, IH), 7.30 (d, IH), 7.10 (d, IH), 4.15 (m, 2H), 3.04 (dd, IH), 2.78-2.68(m, 4H), 2.65-2.54(m, 4H), 2.30 (s, 3H), 1.00 (d, 3H)
Preparation of fEH-f6-methyl-pyridin-2-yO-ethanone 0-{3-[6-f 1-hydroxy-ethyO-pyridin-
2-yl1-2-methyl-propyl>-oxime
Figure imgf000143_0001
l-(6-{(E)-2-Methyl-3-[l-(6-methyl-pyridin-2-yl)-eth-(E)-ylideneaminooxy]-propenyl}- pyridin-2-yl)-ethanone (149mg) was dissolved in ethanol (8ml_). Palladium (5% on charcoal; lOmg) was added and the reaction mixture was stirred for 16h under an atmosphere of hydrogen. The reaction mixture was filtered, evaporated and purified over silica to give a yellow oil (32mg). JH-NMR (CDCI3, 400 MHz):7.65 (d, IH), 7.6-7.5 (m, 2H), 7.10-7.03 (m, 3H), 4.89-4.79 (m, 2H), 4.18-4.05 (m, 2H), 2.98 (dd, IH), 2.68 (m, IH), 2.55 (m, 4H), 2.30 (d, 3H), 1.49 (dd, 2H), 1.00 (dd, 3H)
Preparation of l-r6- rE)-2-methyl-3-ri-r6-methyl-pyridin-2-yn-ethylideneaminooxy1- propenyl>-pyridin-2-yn-ethanone
Figure imgf000143_0002
(E)-l-(6-Methyl-pyridin-2-yl)-ethanone 0-{(E/Z)-2-methyl-3-[6-(2-methyl-[l,3]dioxolan- 2-yl)-pyridin-2-yl]-allyl}-oxime (540mg; containing some (E)-l-(6-methyl-pyridin-2-yl)- ethanone oxime) was dissolved in acetone (20ml_). Hydrochloric acid (3ml_; 30% aqueous solution) was added and the reaction mixture was stirred at ambient temperature for 72h. The reaction mixture was concentrated, neutralised with sodium bicarbonate (20% aqueous solution) and extracted with dichloromethane. The organic phase was dried over sodium sulphate, concentrated and purified by chromatography over silica to give a yellow oil (189mg). According to JH-NMR a mixture of E/Z isomers was obtained. JH-NMR (CDCI3, 400 MHz) signals for E/E isomer: 7.86 (d, IH), 7.77 (t, IH), 7.69 (d, IH), 7.55 (t, IH), 7.38 (d, IH), 6.68 (s, IH), 7.10 (d, IH), 6.60 (s, IH), 4.85 (s, 2H), 2.74 (s, 3H), 2.57 (s, 3H), 2.42 (s, 3H), 2.32 (s, 3H). Preparation of fEM-f6-methyl-pyridin-2-yO-ethanone 0-{2-methyl-3-r6-f2-methyl- rif3 dioxolan-2-yn-pyridin-2-yn-allyl>-oxime
Figure imgf000144_0001
Sodium hydride (0.17g; 55% w/w in mineral oil) was added at 0-5°C to a solution of (E)-l-(6-methyl-pyridin-2-yl)-ethanone oxime (0.59g) in dimethylformamide (12ml_). After stirring for 30min at 0-5°C a solution of methanesulfonic acid 2-methyl-3-[6-(2-methyl- [l,3]dioxolan-2-yl)-pyridin-2-yl]-allyl ester (0.456g) in dimethylformamide (4mL) was added. The cooling bath was removed and the reaction mixture was stirre for 16h at ambient temperature. The reaction mixture was diluted with ethyl acetate and washed with water. The organic phase was dried over sodium sulphate, concentrated and purified by
chromatography over silica to give a yellow oil (672 mg), which still contained some (E)-l- (6-methyl-pyridin-2-yl)-ethanone oxime. This material was used in the next step without further purification.
Preparation of methanesulfonic acid 2-methyl-3-r6-(2-methyl-ri,31dioxolan-2-v0-pyridin-
2-yll-allyl ester
Figure imgf000144_0002
Methane sulfonyl chloride (0.498g) was added at 0-5°C to a solution of (E)-2-methyl-3- [6-(2-methyl-[l,3]dioxolan-2-yl)-pyridin-2-yl]-prop-2-en-l-ol (0.93g) and triethylamine (1.09g) in dichloromethane (15ml_). After stirring for 2h at 0-5°C sodium bicarbonate (2ml_, 20% aqueous solution) was added. The reaction mixture was diluted with dichloromethane, washed with water, dried over magnesium sulfate, filtrated and concentrated to give a yellow oil (0.45g) which was used in the next step without further purification. ^-NMR (CDCI3, 400 MHz) signals for E isomer:7.68 (t, IH), 7.41 (d, IH), 7.19 (d, IH), 6.68 (s, IH), 4.79 (s, 2H), 4.10 (m, 2H), 3.93 (m, 2H), 3.07 (s, 3H), 2.23 (s, 3H), 1.78 (s, 3H). Preparation of rEV2-methyl-3-r6-r2-methyl-rif31dioxolan-2-yn-pyndin-2-yn-prop-2-en-l- ol
Figure imgf000145_0001
Diisobutyl aluminium hydride (1M in dichloromethane; 12.4ml_) was added within 30min at -60°C to a solution of 2-methyl-3-[6-(2-methyl-[l,3]dioxolan-2-yl)-pyridin-2-yl]-acrylic acid ethyl ester (1.69g) in dichloromethane (30ml_). After stirring for 3h at -60°C the cooling bath was removed and water (0.5ml_), NaOH (2M aqueous solution; 0.5ml_) and again water (lmL) were added. During these additions the temperature raised to 10°C. The reaction mixture was stirred for 30min at 0-10°C, and then magnesium sulphate was added. After further stirring for 30min the reaction mixture was filtered, evaporated and purified over silica to give a yellow oil (910mg). ^-NMR (CDCI3, 400 MHz):7.64 (t, IH), 7.48 (d, IH), 7.17 (d, IH), 6.63 (s, IH), 4.22 (d, 2H), 4.10 (m, 2H), 3.92 (m, 2H), 2.14 (s, 3H), 1.78 (s, 3H).
Preparation of 2-methyl-3-r6-r2-methyl-rif31dioxolan-2-yn-pyridin-2-yl1-acrylic acid ethyl
Figure imgf000145_0002
2-(Diethoxy-phosphoryl)-propionic acid ethyl ester (2.52g) and diisopropylethylamine (1.74g) were added at ambient temperature to a solution of lithium chloride (0.54g) in acetonitrile (30ml_). After stirring for 5 min a solution of 6-(2-methyl-[l,3]dioxolan-2-yl)- pyridine-2-carbaldehyde (1.2g; prepared according to Bioorganic & Medicinal Chemistry (2005), 13(24), 6763-6770) in acetonitrile (5ml_) was added and the reaction mixture was stirrer for 72h at ambient temperature. The reaction mixture was diluted with ethyl acetate and washed with water. The organic phase was dried over sodium sulphate, concentrated and purified by chromatography over silica to give a yellow oil (1.69g). 1H-NMR (CDCI3, 400 MHz):7.71 (t, IH), 7.67 (s, IH), 7.47 (d, IH), 7.31 (d, IH), 4.28 (q, 2H), 4.13 (m, 2H), 3.95 (m, 2H), 2.46 (s, 3H), 1.79 (s, 3H), 1.35 (t, 3H) Preparation of fEM-f6-methyl-pyridin-2-yO-ethanone oxime
Figure imgf000146_0001
2-Acetyl-6-methyl-pyridine (12g) was dissolved in methanol (70ml_). Sodium acetate (10.9) and hydroxylamine hydrochloride (7.4g) were added. After stirring for 3h at ambient temperature the reaction mixture was diluted with ethyl acetate washed with water, dried over sodium sulphate, filtered, evaporated and crystallised from hexane to give a white solid (11.2g). ^-NMR (CDCI3, 400 MHz):9.95 (s broad, 1H), 7.57 (m, 2H), 7.10 (d, 1H), 2.59 (s, 3H), 2.40 (s, 3H).
Example 4: Preparation of compounds P.07 and P.08
Figure imgf000146_0002
2-Methoxy-phenyl boronic-acid (56mg), palladium (II) acetate (2mg), 2- dicyclohexylphosphino-2',6'-dimethoxybiphenyl (sPhos; 8mg), potassium phosphate (236mg) and (E)-l-(6-{3-[l-(6-bromo-pyridin-2-yl)-eth-(E)-ylideneaminooxy]-propyl}-pyridin-2-yl)- ethanone O-methyl-oxime(lOOmg) were suspended in toluene (5ml_) and stirred under an argon atmosphere at 100°C for 16h. The reaction mixture was diluted with ethyl acetate and washed with water. The organic phase was separated dried over sodium sulphate and concentrated. The crude was purified by chromatography over silica to give a colorless oil (59mg). ^-NMR (CDCI3, 400 MHz):7.95 (d, 1H), 7.85 (m, 2H), 7.68 (m, 2H), 7.76 (t, 1H), 7.48 (t, 1H), 7.10 (m, 2H), 7.00 (d, 1H), 4.30 (t, 2H), 4.02 (s, 3H), 3.89 (s, 3H), 2.93 (t, 2H), 2.40 (s, 3H), 2.33 (s, 3H), 2.24 (m, 2H).
Preparation of (E^-l-Ce- S-ri-Ce-bromo-pyridin^-vn-eth-CE^-ylideneaminooxyl-propyIV pyridin-2-vD-ethanone O-methyl-oxime
Figure imgf000146_0003
(E)-l-(6-Bromo-pyridin-2-yl)-ethanone 0-[3-(6-{l-[(E)-methoxyimino]-ethyl}-pyridin-2- yl)-prop-2-ynyl]-oxime (883mg) was dissolved in ethanol (20ml_). Platinum (IV) oxide hydrate (73mg) was added and the reaction mixture was stirred for 30min under an atmosphere of hydrogen. The reaction mixture was filtered, evaporated and purified over silica to give a yellow oil (871mg). ^-NMR (CDCI3, 400 MHz):7.87 (d, IH), 7.70 (d, IH), 7.56 (t, IH), 7.50 (t, IH), 7.41 (d, IH), 7.11 (d, IH), 4.30 (t, 2H), 4.01 (s, 3H), 2.92 (t, 2H), 2.32 (s, 3H), 2.29 (s, 3H), 2.22 (m, 2H)
Preparation of fEH-f6-bromo-pyridin-2-yO-ethanone 0-r3-f6-n-rfE>methoxyimino1- ethyl>- ridin-2-yn-prop-2-ynyn-oxime
Figure imgf000147_0001
Sodium bis-trimethylsilyl amide 2M in tetrahydrofuran (3.63ml_) was added at 0-5°C to a solution of (E)-l-(6-bromo-pyridin-2-yl)-ethanone oxime (1.3g) in acetonitrile (35ml_) and dimethylformamide (5ml_). After stirring for 20min at ambient temperature a solution of methanesulfonic acid 3-(6-{l-[(E)-methoxyimino]-ethyl}-pyridin-2-yl)-prop-2-ynyl ester (1.7g) in dimethylformamide (5ml_) was added. The reaction mixture was the stirred for 16h at ambient temperature diluted with ethyl acetate and washed with water. The organic phase was separated dried over sodium sulphate and concentrated. The crude was purified by chromatography over silica to give a yellow solid (l.Og). ^-NMR (CDCI3, 400 MHz):7.93 (d, IH), 7.88 (d, IH), 7.62 (t, IH), 7.53 (t, IH), 7.44 (t, IH), 5.18 (s, 2H), 4.02 (s, 3H), 2.35 (s, 3H), 2.32 (s, 3H).
Pre aration of fEVl-f6-bromo-pyridin-2-yO-ethanone oxime
Figure imgf000147_0002
2-Bromo-6-methyl-pyridine (2.5g) was dissolved in methanol (40ml_). Sodium acetate (1.54g) and hydroxylamine hydrochloride (1.04g) were added. After stirring for 24h at ambient temperature the reaction mixture was diluted with ethyl acetate, washed with water, dried over sodium sulphate, filtered and the solvent evaporated to give a white solid (2.5g). ^-NMR (DMSO, d6, 400 MHz): 11.75 (s, IH), 7.88 (d, IH), 7.76 (t, IH), 7.63. Example 5: Preparation of compound P.23
Figure imgf000148_0001
Sodium acetate (65mg) and 0-methyl-hydroxylamine hydrochloride (65mg) were added 5 to a solution of 2-methyl-l-(6-{3-[l-(6-methyl-pyridin-2-yl)-eth-(E)-ylideneaminooxy]- propyl}-pyridin-2-yl)-propan-l-one (40mg) in methanol (4mL). After stirring for 72h at ambient temperature the reaction mixture was diluted with ehylacetate washed with water and dried over sodium sulfate. Filtration, concentration and purification by chromatography over silica gave a 1:3 mixture of A:B (17mg) and A (8mg). ^-NMR (Compound A; CDCI3, 10 400 MHz): 7.66 (d, IH), 7.55(m, 2H), 7.42 (d, IH), 7.09 (m, 2H), 4.28 (t, 2H), 3.97 (s, 3H), 3.69 (m, IH), 2.91 (t, 2H), 2.58 (s, 3H), 2.32 (s, 3H), 2.20 (m, 2H), 1.28(d, 6H).
Preparation of 2-methyl-l-(,6- 3-ri-(,6-methyl-pyridin-2-vn-eth-(E)-ylideneaminooxy1- propyl}-pyridin-2-v0-propan-l-one
Figure imgf000148_0002
l,l,l-Tris(acetyloxy)-l,l-dihydro-l,2-benziodoxol-3-(lH)-one (89mg) was added to a solution of (E)-l-(6-methyl-pyridin-2-yl)-ethanone 0-{3-[6-(l-hydroxy-2-methyl-propyl)- pyridin-2-yl]-propyl}-oxime (60mg) in dichloromethane (5ml_). After stirring for 4h at
20 ambient temperature sodium hydrogen carbonate (2ml_; 20% aqueous solution) and sodium thiosulphate (2ml_; 30% aqueous solution) were added. After stirring for further 40min the organic phase was separated, washed with water, dried over sodium sulphate, filtered and purified by chromatography over silica to give a colorless oil (40mg). ^-NMR (CDCI3, 400 MHz):7.85 (d, IH), 7.70 (m, 2H), 7.55 (t, IH), 7.32 (d, IH), 7.10 (d, IH), 4.30 (t, 2H), 4.16
25 (m, IH), 3.00 (t, 2H), 2.56 (s, 3H), 2.32 (s, 3H), 2.25 (m, 2H), 1.20 (d, 6H). Preparation of fEM-f6-methyl-pyridin-2-yO-ethanone 0-{3-[6-f l-hydroxy-2-methyl- propyn-pyridin-2-yn-propyl>-oxime
Figure imgf000149_0001
Isopropyl magnesium chloride (2M in tetrahydrofuran; 0.355ml_) was added at -70°C to a solution of 6-{3-[l-(6-methyl-pyridin-2-yl)-eth-(E)-ylideneaminooxy]-propyl}-pyridine-2- carbaldehyde (190mg) in tetrahydrofuran (lOmL). After stirring for 90min at - 70°C ammonium chloride (10% aqueous solution; ImL) was added. The reaction mixture was the stirred for lOmin diluted with ethyl acetate and washed with water. The organic phase was separated, dried over sodium sulphate and concentrated. The crude was purified by chromatography over silica to give a yellow oil (60mg). ^-NMR (CDCI3, 400 MHz): 7.67 (d, 1H), 7.55 (m, 2H), 7.18 (m, 2H), 7.00 (d, 1H), 4.62 (d,broad, 1H), 4.53 (m, 1H), 4.76 (t, 2H), 2.92 (t, 2H), 2.56 (s, 3H), 2.32 (s, 3H), 2.20 (m, 2H), 2.00 (m, 1H), 1.02 (d, 3H), 0.75 (d, 3H).
Preparation of 6- 3-ri-(,6-methyl-pyridin-2-vn-eth-(E)-ylideneaminooxy1-propyl>- pyridine-2-carbaldehvde
Figure imgf000149_0002
6-{3-[l-(6-Methyl-pyridin-2-yl)-eth-(E)-ylideneaminooxy]-prop-l-ynyl}-pyridine-2- carbaldehyde (1.13g) was dissolved in ethanol (40ml_). Platinum (IV) oxide hydrate (80mg) was added and the reaction mixture was stirred for 3h under an atmosphere of hydrogen. The reaction mixture was filtered, evaporated and purified over silica to give a yellow oil (235mg). ^-NMR (CDCI3, 400 MHz): 10.05 (s, 1H), 7.79 (m, 2H), 7.67 (d, 1H), 7.54 (t, 1H), 7.42 (d, 1H), 7.10 (d, 1H), 4.30 (t, 2H), 3.03 (t, 2H), 2.47 (s, 3H), 2.31 (s, 3H), 2.25 (m,
2H). Preparation of 6-{3-ri-r6-methyl-pyndin-2-ylVeth-rEVylideneaminooxy1-prop-l-ynyl>- pyridine-2-carbaldehyde
Figure imgf000150_0001
6-Bromo-pyridine-2-carbaldehyde (2.5g) and (E)-l-(6-methyl-pyridin-2-yl)-ethanone O-prop- 2-ynyl-oxime (2.53g) were dissolved in THF (80ml_). Diisopropylamine (3.79mL), dichlorobis (tri phenyl phospine) palladium (II) (283mg) and copper (I) iodide (205mg) were added. After stirring for 6h at ambient temperature the reaction mixture was diluted with ethyl acetate washed with sodium bicarbonate (10% aqueous solution), water and brine. The organic phase was dried over sodium sulphate, concentrated and purified by chromatography over silica to give a beige solid (3.0g). ^-NMR (CDCI3, 400 MHz): 10.05 (s, 1H), 7.90 (d, 1H), 7.85 (t, 1H), 7.70 (m, 2H), 7.55(t, 1H), 7.12 (d, 1H), 5.10 (s, 2H), 2.68 (s, 3H), 2.40 (s, 3H).
Example 6: Preparation of compound P.06
Figure imgf000150_0002
(E)-l-(6-{l-Methylene-3-[l-(6-methyl-pyridin-2-yl)-eth-(E)-ylideneaminooxy]-propyl}- pyridin-2-yl)-ethanone O-methyl-oxime (76mg) was dissolved in ethanol (lOmL). Palladium (5% on charcoal; lOmg) was added and the reaction mixture was stirred for 2h under an atmosphere of hydrogen. The reaction mixture was filtered, evaporated and purified over silica to give a colorless oil (75mg).
Preparation of (E)-l-(6- i-methylene-3-ri-(6-methyl-pyndin-2-vn-eth-(E)- ylideneaminoox -propyl}-pyridin-2-vD-ethanone O-methyl-oxime
Figure imgf000150_0003
Sodium acetate (26mg) and O-methyl-hydroxylamine hydrochloride (24mg) were added to a solution of l-(6-{l-methylene-3-[l-(6-methyl-pyridin-2-yl)-eth-(E)-ylideneaminooxy]- propyl}-pyridin-2-yl)-ethanone (78mg) in methanol (4ml_). After stirring for 16h at ambient temperature the reaction mixture was diluted with ethyl acetate, washed with water and dried over sodium sulphate. Filtration and concentration gave a colorless oil (80mg). IH-NMR (CDCI3, 400 MHz): 7.80 (d, 1H) 7.70-7.60 (m, 2H), 7.53 (m, 2H), 7.09 (d, 1H), 5.89 (s, 1H),4.90 (s, 1H), 4.44 (t, 2H),4.03 (s, 3H), 3.10 (t, 2H), 2.55 (s, 3H), 2.45 (s, 3H), 2.28(s, 3H).
Preparation of l-r6-n-methylene-3-ri-r6-methyl-pyndin-2-ylVeth-rEVylideneaminooxy1- ropyl >-pyridin-2-yn-ethanone
Figure imgf000151_0001
(E)-l-(6-Methyl-pyridin-2-yl)-ethanone 0-{3-[6-(2-methyl-[l,3]dioxolan-2-yl)-pyridin-2- yl]-but-3-enyl}-oxime (230mg; 70% purity) was dissolved in acetone (15ml_). Hydrochloric acid (2.5ml_; 10% aqueous solution) was added and the reaction mixture was stirred at ambient temperature for 16h. The reaction mixture was concentrated, neutralised with sodium bicarbonate (20% in water) and extracted with dichloromethane. The organic phase was dried over sodium sulphate, concentrated and purified by chromatography over silica to give a yellow oil (86mg). 1H-NMR (CDCI3, 400 MHz): 7.91 (d, 1H) 7.75 (m, 2H), 7.66 (d, 1H), 7.54 (t, 1H), 7.09 (d, 1H), 5.92 (s, 1H),4.98 (s, 1H), 4.47 (t, 2H), 3.15 (t, 2H), 2.64 (s, 3H), 2.56 (s, 3H), 2.27(s, 3H).
Preparation of fEH-f6-methyl-pyridin-2-yO-ethanone CH"3-r6-f2-methyl-rif31dioxolan-
2-ylVpyridin-2-yn-but-3-enyl}-oxime
Figure imgf000151_0002
Butyl lithium (1.6M in hexane; 1.27ml_) was added at -70°C to a solution of
methyltriphenyl phosphonium bromide in tetrahydrofuran (8ml_). The reaction mixture was stirred for 30min at -70°C, heated up to ambient temperature, and cooled again to -70°C. A solution of l-[6-(2-methyl-[l,3]dioxolan-2-yl)-pyridin-2-yl]-3-[l-(6-methyl-pyridin-2-yl)-eth- (E)-lideneaminooxy]-propan-l-one (300mg; 80% purity) in tetrahydrofuran (5ml_) was added. The reaction mixture was stirred for lh at -70°C and 2h at ambient temperature. The reaction mixture was quenched with water and diluted with ethyl acetate. The organic phase was washed with water, separated, dried over sodium sulphate and concentrated. The residue was purified by chromatography over silica to give a yellow oil (230mg; 70% purity). This material was used in the next step without further purification. Preparation of l-r6-r2-methyl-rif31dioxolan-2-yl>pyndin-2-yn-3-ri-r6-metriyl-pyndin-2- ylVeth-fEVIideneaminooxyl-propan-l-one
Figure imgf000152_0001
Manganese dioxide (5.2g) was added to a solution of (E)-l-(6-methyl-pyridin-2-yl)- ethanone 0-{3-hydroxy-3-[6-(2-methyl-[l,3]dioxolan-2-yl)-pyridin-2-yl]-propyl}-oxime (1.46g) in dichloromethane (30mL). After stirring for 16h at ambient temperature the reaction mixture was filtered over hyflo, concentrated and the residue was purified by chromatography over silica to give a yellow oil (470mg; 80% purity). This material was used in the next step without further purification.
Preparation of (EH-(6-methyl-pyridin-2-vO-ethanone 0-{3-hydrOxy-3-r6-(2-methyl- ri,31dioxolan-2-yl>pyridin-2-yl1-propyl}-oxime
Figure imgf000152_0002
Butyllithium (1.6M in hexane; 4.18ml_) was added within lOmin at -60°C to a solution of 2-bromo-6-(2-methyl-[l,3]dioxolan-2-yl)-pyridine (1.6g) in tetrahydrofuran (24ml_). After stirring for lh at -60°C 3-[l-(6-methyl-pyridin-2-yl)-eth-(E)-ylideneaminooxy]- propionaldehyde (1.35g) was added. The reaction mixture was stirred for lh at -60°C. Then ammonium chloride (6ml_; 10% aqueous solution) was added, the cooling bath was removed and the reaction mixture was diluted with ethyl acetate. The organic phase was washed with water, separated and dried over sodium sulphate and concentrated. The residue was purified by chromatography over silica to give a yellow oil (1.46g). 1H-NMR (CDCI3, 400 MHz): 7.70 (m, 2H), 7.56 (t, 1H), 7.48 (d, 1H), 7.28 (d, 1H), 7.10 (d, 1H), 5.00 (m, 1H), 4.55-4.38 (m, 3H), 4.12 (m, 2H), 3.90 (m, 2H), 2.59 (s, 3H), 2.47 (m, 1H), 2.30(s, 3H), 2.12 (m, 1H), 1.78 (s, 3H).
Preparation of 3-ri-(,6-methyl-pyridin-2-vn-eth-(E)-ylideneaminooxy1-propionaldehvde
Figure imgf000152_0003
A solution of l,l,l-tris(acetyloxy)-l,l-dihydro-l,2-benziodoxol-3-(lH)-one (4.21g) and (E)-l-(6-methyl-pyridin-2-yl)-ethanone 0-(3-hydroxy-propyl)-oxime (1.88g) in dichloromethane (55ml_) was added dropwise to dichloromethane (180ml_) and
water(0.3ml_). After stirring for lh at ambient temperature, sodium hydrogen carbonate (2ml_; 20% aqueous solution) and sodium thiosulphate (2ml_; 30% aqueous solution) were added. After stirring for further 40min the organic phase was separated, washed with water, dried over sodium sulphate, filtered, concentrated and purified by chromatography over silica to give a yellow oil (1.38g). 1H-NMR (CDCI3, 400 MHz): 9.90 (s, IH), 7.63 (d, IH), 7.58 (t, IH), 7.12 (d, IH), 4.59 (t, 2H), 2.84 (m, 2H), 2.58 (s, 3H), 2.33(s, 3H).
Preparation of fEH-f6-methyl-pyridin-2-yO-ethanone C 3-hydroxy-propyn-oxime
Figure imgf000153_0001
Sodium hydride (55% in mineral oil; 640mg) was added at 0-5°C to a solution of (E)-l- (6-methyl-pyridin-2-yl)-ethanone oxime (2.0g) in dimethylformamide (35ml_). After stirring for 20min at 0-5°C 3-bromo propanol (2.78g) was added. The reaction mixture was the stirred for 3h at ambient temperature diluted with ethyl acetate and washed with water. The organic phase was separated, dried over sodium sulphate and concentrated. The residue was purified by chromatography over silica to give a colorless oil (1.8g). 1H-NMR (CDCI3, 400 MHz): 7.65 (d, IH), 7.58 (t, IH), 7.12 (d, IH), 4.40 (t, 2H), 3.84 (m, 2H), 2.60 (s, 3H), 2.34(s, 3H), 2.16 (s, broad, IH), 2.03 (m, 2H).
Example 7: Preparation of compound P.10
Figure imgf000153_0002
l-(4,6-Dimethyl-pyridin-2-yl)-ethanone (400mg) was dissolved in methanol (15ml_) and (E)-l-[6-(3-aminooxy-propyl)-pyridin-2-yl]-ethanone O-methyl-oxime (600mg) was added. After stirring for 70h at ambient temperature, the reaction mixture was concentrated and the residue was purified by chromatography over silica to give colorless oil (740mg). ^-NMR (CDCI3, 400 MHz):7.70 (d, IH), 7.55 (t, IH), 7.47 (s, 2H), 7.11 (d, IH), 6.93 (s, IH), 4.28 (t, 2H), 4.01 (s, 3H), 2.92 (t, 2H), 2.51 (s, 3H), 2.32 (s+s+s, 9H), 2.21 (m, 2H) Preparation of fEH-r6-f3-aminooxy-propyO-pyridin-2-yn-ethanone O-methyl-oxime
Figure imgf000154_0001
Hydrazine monohydrate (1.65mL) was added dropwise to a suspension of 2-[3-(6-{l- [(E)-methoxyimino]-ethyl}-pyridin-2-yl)-propoxy]-isoindole-l,3-dione (6g) in ethanol (40ml_). After stirring for 2 h at ambient temperature The reaction mixture was poured on water and then NaOH (4M aqueous solution) was added till the pH was 14. The basic solution was extracted twice with ethyl acetate. The combined organic layers were washed with water, brine and then dried over sodium sulphate, filtrated and evaporated. The residue was purified by chromatography over silica (Eluent: cyclohexane:ethyl acetate 1: 1) to give a colorless oil (3.2g). IH-NMR (CDCI3, 400 MHz): 7.70 (d, IH), 7.55 (t, IH), 7.09 (d, IH), 5.37 (s, broad, 2H), 4.03 (s, 3H), 3.73 (t, 2H), 2.85 (t, 2H), 2.32 (s, 3H), 2.06 (m, 2H).
Preparation of 2-r3-r6- i-rrE)-methoxyimino1-ethyl>-pyridin-2-yn-propoxy1-isoindole- 1,3-dione
Figure imgf000154_0002
Palladium on carbon (5% on charcoal; 800mg) was added to a solution of 2-[3-(6-{l- [(E)-methoxyimino]-ethyl}-pyridin-2-yl)-prop-2-ynyloxy]-isoindole-l,3-dione(8g) in tetrahydrofuran. After stirring for 3.5 h under an atmosphere of hydrogen the reaction mixture was filtered, the filtrate was concentrated and the residue was purified by chromatography over silica (Eluent: cyclohexane: ethyl acetate) to give a white solid (6.4g). mp. 65-68°C; IH-NMR (CDCI3, 400 MHz): 7.85 (m, 2H), 7.75 (m, 3H), 7.59 (t, IH), 7.20 (d, IH), 4.28 (t, 2H), 4.01 (s, 3H), 3.05 (t, 2H), 2.29 (s, 3H), 2.25 (m, 2H).
Preparation of 2-r3-r6- i-rrE)-methoxyimino1-ethyl>-pyridin-2-yn-prop-2-ynyloxy1- isoindole-l,3-dione
Figure imgf000154_0003
N-hydroxyphthalimide (6.4g) and triphenylphosphine (11.3g) were added portion wise at 5°C to a solution of (E)-l-[6-(3-Hydroxy-prop-l-ynyl)-pyridin-2-yl]-ethanone O-methyl-oxime (8.0g) in tetrahydrofuran (60ml_). To this suspension a solution of
diisopropylazodicarboxylate (8.8ml_) in tetrahydrofuran (lOmL) was added at 5 - 10°C within 70 min. The reaction mixture was diluted with tetrahydrofuran (lOOmL). After stirring for a further 2.5 h at 5-10°C the reaction mixture was concentrated. The beige residue was suspended in methanol: water (5: 1; 250ml_) and stirred for 10 min. The precipitate was filtered, washed with methanol: water (5: 1; 200ml_) and dried to give a white solid (12.3g; mp. 185-188°C)
1H-NMR (CDCI3, 400 MHz): 7.86 (m, 3H), 7.78 (m, 2H), 7.62 (t, 1H), 7.42 (d, 1H), 5.13 (s, 2H), 4.01 (s, 3H), 2.24 (s, 3H).
Example 9: Preparation of compound P.55
Figure imgf000155_0001
To a stirred solution of (E)-l-[6-(3-aminooxy-propyl)-pyridin-2-yl]-ethanone O- methyl-oxime (160 mg; 0.71 mmol) in methanol (15 ml.) was added 9-methyl-2,3-dihydro- lH-acridin-4-one (150 mg; 0.71 mmol). After being stirred for 3 hours at room temperature methanol was removed in vacuo to give a colourless oil (320 mg). The crude material was purified by chromatography (Supeico 25 g silica gel; eluent: 40 % cyclohexane in ethylacetate), to yield 250 mg (84% of theory) of the title compound as a colourless oil. LC-MS (ZCQ): UV Detection: 220 nm; f¾ = 1.69 min. MS: (M++l) = 417, (M++23) = 439.
Example 10: Preparation of compound P.56
Figure imgf000155_0002
A solution of (E)-l-[6-(3-aminooxy-propyl)-pyridin-2-yl]-ethanone O-methyl-oxime
(80.0 mg) in absolute ethanol (0.50 ml.) was charged to a 5 ml. Supeico vial. Under magnetic stirring, p-toluenesulphonic acid mono-hydrate (4.0 mg) was added, followed by the addition of 6,7-dihydro-2-methoxy- 8(5H)-quinolinone (63 mg). The Supeico vial is then sealed with a septum cap. The resulting light-yellow solution was stirred at room temperature for 3 hours. TLC indicated that no starting materials were remaining after this time. The ethanol was removed in vacuo. A saturated aqueous solution of NaHC03 (2.00 mL) was added to the resulting residue, and extraction was carried out using ethyl acetate (2x5 mL). The combined organic layers were washed with brine, dried over sodium sulphate and filtered. The solvent was removed in vacuo to give an orange oil (139 mg). No further purification was required.
LC-MS (ZCQ): UV Detection: 220 nm; f¾ = 1.52 min. MS: (M++l) = 383, (M++23) = 405. TLC: Plates: Merck DC-Plates, silica gel F254, saturated atmosphere in developing tank, UV detection, eluent: heptane/ethyl acetate 1 :2 (v:v); Rf of title compound = 0.54, Rf of ketone starting material = 0.33, Rf of oxyamine starting material = 0.26.
Example 11: Preparation of compound P.57
Figure imgf000156_0001
In a 25 mL single-necked round-bottomed flask, Palladium on carbon (10% on charcoal; 13 mg) was added to a solution of 2-methyl-6,7-dihydro-5H-quinolin-8-one 0-[3-(6-{l-[(E methoxyimino]-ethyl}-pyridin-2-yl)-prop-2-ynyl]-oxime (130 mg) in ethanol. After stirring for 3.5 h under an atmosphere of hydrogen (normal pressure) the reaction mixture was filtered, the filtrate was concentrated and the residue was purified by chromatography over silica (Eluent: heptane:ethyl acetate 9: 1 (v/v)) to give a colourless oil (80 mg).
LC-MS (ZCQ): UV Detection: 220 nm; l¾ = 1.42 min. MS: (M++l) = 367, (M++23) = 389. TLC: Plates: Merck DC-Plates, silica gel F25 , saturated atmosphere in developing tank, UV detection, eluent: heptane/ethyl acetate 1 : 1 (v:v); Rf of title compound = 0.37, Rf of oxyamine starting material = 0.27.
Preparation of 2-methyl-6,7-dihvdro-5H-quinolin-8-one Q-r3-(6-{l-r(E)-methoxyimino1- ethyl}-pyndin-2-yl>prop-2-vnyl1-oxime
Figure imgf000157_0001
A solution of (E)-l-[6-(3-aminooxy-prop-l-ynyl)-pyridin-2-yl]-ethanone O-methyl-oxime (131 mg) in absolute ethanol (5.0 mL) was charged to a 25 single-necked round-bottomed flask. Under stirring, p-toluenesulphonic acid mono-hydrate (7.0 mg) was added, followed by the addition of 2-methyl-6,7-dihydro-5H-quinolin-8-one (97 mg). The resulting light-yellow solution was stirred at room temperature for 2 hours. TLC indicated that no starting materials were remaining after this time. The ethanol was removed in vacuo. A saturated aqeous solution of NaHC03 (20 mL) was added to the resulting residue, and extraction was carried out using dichloromethane (2x20 mL). The combined organic layers were washed with brine, dried over sodium sulphate and filtered. The solvent was removed in vacuo to give a beige oil (200 mg). The residue was purified by chromatography over silica (Eluent: heptane:ethyl acetate 9: 1) to give a yellow oil (160 mg). LC-MS (ZCQ): UV Detection: 220 nm; f¾ = 1.55 min. MS: (M++l) = 363.
TLC: Plates: Merck DC-Plates, silica gel F254, saturated atmosphere in developing tank, UV detection, eluent: heptane/ethyl acetate 1: 1 (v:v); Rf of title compound = 0.48, Rf of ketone starting material = 0.11, Rf of oxyamine starting material = 0.33.
Preparation of fEn-r6-f3-aminooxy-prop-l-ynyl>pyridin-2-yn-ethanone O-methyl- oxime
Figure imgf000157_0002
In a 25 mL single-necked round-bottomed flask, hydrazine monohydrate (0.23 mL) was added dropwise to a suspension of 2-[3-(6-{l-[(E)-methoxyimino]-ethyl}-pyridin-2-yl)-prop- 2-ynyloxy]-isoindole-l,3-dione (810 mg) in ethanol (5 mL). After stirring for 4 h at ambient temperature the reaction mixture was poured on water and then NaOH (4M aqueous solution) was added until the pH was 14. The basic solution was extracted twice with ethyl acetate. The combined organic layers were washed with water, brine and then dried over sodium sulphate, filtrated and concentrated in vacuo. The residue was purified by chromatography over silica (Eluent: heptane:ethyl acetate 4: 1) to give a beige solid (330 mg; m.p. 60 to 63 °C).
LC-MS (ZCQ): UV Detection: 220 nm; f¾ = 1.33 min. MS: (M++l) = 220, (M++23) = 242. TLC: Plates: Merck DC-Plates, silica gel F254, saturated atmosphere in developing tank, UV detection, eluent: heptane/ethyl acetate 1: 1 (v:v); Rf of title compound = 0.49, Rf of phthalimide starting material = 0.19.
Example 12: Preparation of compound P.60
Figure imgf000158_0001
2-Methyl-6,7-dihydro-5H-quinazolin-8-one (lOOmg; 0.6mmol)) was dissolved in methanol (13ml_) and (E)-l-[6-(3-aminooxy-propyl)-pyridin-2-yl]-ethanone O-methyl-oxime (138mg; 0.6mmol) was added. After stirring for 18h at ambient temperature, the reaction mixture was concentrated and the residue was purified by chromatography over silica (combiflash RF, 0-80% ethylacetate in cyclohexane) to give 2-Methyl-6,7-dihydro-5H- quinazolin-8-one 0-[3-(6-(l-((E)-methoxyimino)-ethyl)-pyridin-2-yl)-propyl]-oxime as a light yellow oil (115mg; 51% of theory). LC-MS (Method ZCQ) Rt = 1.70 min., MS: (M++l) = 368. JH-NMR (CDCI3, 400 MHz): 1.85 (m,2H); 2.23 (m, 2H); 2.30 (s, 3H); 2.68 (t, 2H); 2.78 (s, 3H); 2.81 (t, 2H); 2.92 (m, 2H); 4.01 (s, 3H), 4.45 (t, 2H); 7.13 (d, IH); 7.56 (t, IH); 7.71 (d, IH); 8.49 (s, IH).
Pre aration of 2-methyl-6f7-dihydro-5H-quinazolin-8-one
Figure imgf000158_0002
In a 25ml_ single-necked round-bottomed flask, equipped with a condenser 8-Ethoxy-2- methyl-5,6-dihydro-quinazoline (1.30 g; 6.80 mmol) is dissolved in a mixture of acetic acid (31 mL) and water (3.1 mL). Stirring was continued under heating to reflux over night for 20 hours. TLC indicated that starting materials were consumed by this time. The mixture was cooled to room temperature, water and saturated NaHC03 was added. Extraction was carried out using dichloromethane (3x100 mL). The combined organic phases were washed with brine and then dried over sodium sulphate, filtered and the solvent was removed in vacuo. The crude is purified via chromatography (combiflash RF, 0-10% methanol in dichloromethane) to give 2-Methyl-6,7-dihydro-5H-quinazolin-8-one (764 mg; 69% of theory)as a brown oil. LC-MS (Method ZCQ) Rt = 0.91 min., MS: (M++l) = 163. JH-NMR (CDCI3, 400 MHz): 2.24 (m, 2H); 2.83 (m, 2H); 2.84 (s, 3H); 3.01 (m, 2H); 8.85 (s, 1H).
Pre aration of 8-Ethoxy-2-methyl-5f6-dihydro-quinazoline
Figure imgf000159_0001
In a 25ml_ single-necked round-bottomed flask, equipped with a condenser a mixture of 6-[l-Dimethylamino-meth-(E)-ylidene]-2-ethoxy-cyclohex-2-enone (WO 2004/104007) (2.80 g; 14.3 mmol), Acetamidine hydrochloride (1.70g; 17.9 mmol) and potassium carbonate (2.73g; 19.7 mmol), in absolute ethanol (50 mL) is stirred at reflux temperature over night for 16 hours. The reaction mixture was cooled to room temperature, poured onto water (400ml) and extracted with dichloromethane (3x100 mL). The crude reaction mixture is purified via chromatography (combiflash RF, 70-100% ethylacetate in cyclohexane) to give 8-ethoxy-2-methyl-5,6-dihydro-quinazoline (1.47g, 54% of theory) as brown oil. LC-MS (Method ZCQ) Rt = 1.21 min., MS: (M++l) = 191. JH-NMR (CDCI3, 400 MHz): 1.49 (t, 3H); 2.41 (m, 2H); 2.74 (t, 2H); 2.75 (s, 3H); 3.99 (q, 2H); 5.46 (t,lH); 8.47 (s, 1H).
Example 13: Preparation of compound P.61
Figure imgf000159_0002
2-Phenyl-6,7-dihydro-5H-quinazolin-8-one (lOOmg; 0.45mmol) was dissolved in methanol (lOmL) and (E)-l-[6-(3-aminooxy-propyl)-pyridin-2-yl]-ethanone O-methyl-oxime (lOOmg; 0.45mmol) was added. After stirring for 3 hours at ambient temperature, the reaction mixture was concentrated and the residue was purified by chromatography over silicagel (20g) eluted with (ethylacetate, cyclohexane 2:8) to give 2-Phenyl-6,7-dihydro-5H- quinazolin-8-one 0-[3-(6-(l-((E)-methoxyimino)-ethyl)-pyridin-2-yl)-propyl]-oxime as a colorless oil (130mg; 68% of theory). LC-MS (Method ZMD) Rt = 2.05 min., MS: (M++l) = 430. JH-NMR (CDCI3, 400 MHz): 1.90 (m,2H); 2.23 (m, 2H); 2.31(s, 3H); 2.83 (t, 2H); 2.92 (m, 2H); 4.03 (s, 3H), 4.48 (t, 2H); 7.14 (d, 1H); 7.48 (m, 3H); 7.56 (m, 1H); 7.70 (d, 1H); 8.45 (m, 2H); 8.64 (s, 1H).
Pre aration of 2-Phenyl-6f7-dihydro-5H-quinazolin-8-one
Figure imgf000160_0001
In a 25ml_ single-necked round-bottomed flask, equipped with a condenser 8-Ethoxy-2- phenyl-5,6-dihydro-quinazoline (0.45 g; 1.18 mmol) was dissolved in a mixture of acetic acid (9.5 ml.) and water (0.95 ml_). Stirring was continued under heating to reflux for 15 minutes. TLC indicated that starting materials were consumed by this time. The mixture was cooled to room temperature, water and saturated NaHC03 was added. Extraction was carried out using dichloromethane (3x20 ml_). The combined organic phases were washed with brine and then dried over sodium sulphate, filtered and the solvent was removed in vacuo to give 2-Phenyl- 6,7-dihydro-5H-quinazolin-8-one (380 mg; 95% of theory) as a beige solid. MP: 154-156 °C. LC-MS (Method ZCQ) Rt = 1.49 min., MS: (M++l) = 225. JH-NMR (CDCI3, 400 MHz): 2.25 (m, 2H); 2.86 (m, 2H); 3.03 (m, 2H); 7.51 (m, 3H); 8.52 (m, 2H); 8.94 (s, 1H). Preparation of 8-Ethoxy-2-phenyl-5,6-dihvdro-quinazoline
Figure imgf000160_0002
In a 25ml_ single-necked round-bottomed flask, equipped with a condenser a mixture of 6-[l-Dimethylamino-meth-(E)-ylidene]-2-ethoxy-cyclohex-2-enone (WO 2004/104007) (0.51 g; 2.6mmol) and Benzamidine (0.38 g; 3.2mmol) in absolute ethanol (9ml_) was stirred at reflux temperature over night for 17 hours. The reaction mixture was evaporated to dryness, taken up in dichloromethane and purified via chromatography (combiflash RF, 0-40% ethylacetate in cyclohexane) to give 8-ethoxy-2-phenyl-5,6-dihydro-quinazoline (0.50g, 63% of theory) as a white solid. MP: 101-103°C. LC-MS (Method ZCQ) Rt = 1.84 min, MS: (M+ = 253. JH-NMR (CDCI3, 400 MHz): 1.48 (t, 3H); 2.45 (m, 2H); 2.81 (t, 2H); 4.02 (q, 2H); 5.52 (t,lH); 7.47 (m, 3H); 8.46 (m, 2H); 8.51 (s, 1H).
Example 14: Preparation of compound P.62
Figure imgf000161_0001
To a stirred mixture of (E)-l-[6-(3-aminooxy-propyl)-pyridin-2-yl]-ethanone O-methyl- oxime (150mg; 0.67mmol) and p-TsOH monohydrate (7.6mg; 0.04mmol) in ethanol (lOmL) was added l-(4,6-dimethyl-pyrimidin-2-yl)-ethanone CAS: 64571-50-2 (lOOmg; 0.67mmol) in ethanol (5ml_). After stirring for 2 hours at ambient temperature, the reaction mixture was poured onto water (150ml_) and neutralized by adding triethylamine (a few drops).
Extraction was carried out using dichloromethane (2x50 ml_). The combined organic phases were washed with brine and then dried over sodium sulphate, filtered and the solvent was removed in vacuo. The crude (0.26g oil) is purified via chromatography over silicagel (24g) (combiflash RF, 0-80% ethylacetate in heptane) to give l-(6-(3-[l-(4,6-dimethyl-pyrimidin-2- yl)-eth-(E)-ylideneaminooxy]-propyl)-pyridin-2-yl)-ethanone O-methyl oxime as a colorless resinl (80mg). LC-MS (Method ZCQ) Rt = 1.83 min., MS: (M++l) = 356. JH-NMR (CDCI3, 400 MHz): 2.25 (m,2H); 2.32 (s, 3H); 2.36 (s, 3H); 2.53(s, 3H); 2.96 (t, 2H); 2.92 (m, 2H); 4.03 (s, 3H), 4.47 (t, 2H); 7.00 (s, 1H); 7.14 (d, 1H); 7.48 (t, 1H); 7.72 (d, 1H).
Example 15: Preparation of 2-Methyl-6,7-dihvdro-5H-quinolin-8-one-(E> oxime
Figure imgf000161_0002
A 250 ml. single-necked round-bottomed flask, equipped with a condenser, was charged with a solution of 2-methyl-6,7-dihydro-5H-quinolin-8-one (7.00 g) (CA Registry Number: 849643-01-2) in absolute ethanol (70 ml_). Under stirring, first hydroxylamine-hydrochloride (4.50 g) was added and then a solution of NaOH (8.70g) dissolved in water (14.00ml_) was added in portions. Stirring was continued under heating to reflux for 6.0 hours. Following the course of the reaction by TLC indicated that starting materials were consumed by this time. The suspension was cooled to room temperature. Under stirring and cooling with an ice- water cooling bath, 10 ml. of water was added and the pH was adjusted to 6 by the addition of 6 M aqueous HCI. Extraction was carried out using ethyl acetate (2x100 ml_). The combined organic phases were washed with brine and then dried over sodium sulphate, filtered and the solvent was removed in vacuo to give a yellow solid (7.65 g). LC-MS (Method ZMD) UV Detection: 220 nm; f¾ = 0.20, MS: (M++l) = 177, (M+ +23) = 179; melting point = 177-181 °C.
TLC: Plates: Merck DC-Plates, silica gel F254, saturated atmosphere in developing tank, UV detection, eluent: ethyl acetate/triethylamine 10: 1 (v:v); Rf of title compound = 0.26, Rf of the ketone starting material = 0.46.
The preparation of the following starting materials are described in the literature:
Figure imgf000162_0001
CA Registry Number: 849643-01-2
U.S. Pat. Appl. Publ. (2005), 75 pp., Cont.-in-part of U.S. Ser. No. 437,807. CODEN: USXXCO US 2005075366 Al 20050407
Figure imgf000162_0002
Registry Number: 209741-58-2
WO 199828281 Al (19980702)
Application: WO 97-GB3509 19971222. Priority: GB 96-26742 19961223; GB 97-8115 19970422. CAN 129:95505 AN 1998:479514
Figure imgf000162_0003
Registry Number: 49568-10-7
Hayashi, Eisaku; Suzuki, Senji. Shizuoka Coll. Pharm., Shizuoka, Japan. Yakugaku Zasshi (1975), 95(12), 1439-42. CODEN: YKKZAJ ISSN: 0031-6903
Figure imgf000162_0004
Registry Number: 14428-47-8
Senechal-David, Katell; Hemeryck, Anne; Tancrez, Nicolas; Toupet, Loiec; Williams, J. A. Gareth; Ledoux, Isabelle; Zyss, Joseph; Boucekkine, Abdou; Guegan, Jean-Paul; Le Bozec, Hubert; Maury, Olivier. Laboratoire de Chimie de Coordination et Catalyze, UMR 6509, Institut de Chimie, CNRS-Universite Rennes 1, Rennes, Fr. Journal of the American Chemical Society (2006), 128(37), 12243-12255.
Table 38: ^-NMR data of compounds of formula (Y):
Figure imgf000163_0001
Figure imgf000164_0001
Figure imgf000165_0001
Table 39: LC-MS and mp data for compounds of formula (I)
Figure imgf000166_0001
Figure imgf000167_0001
Figure imgf000168_0001
Figure imgf000169_0001
Figure imgf000170_0001
Figure imgf000171_0001
Figure imgf000172_0001
Figure imgf000173_0001
Figure imgf000174_0001
Figure imgf000175_0001
Figure imgf000176_0001
Figure imgf000177_0001
Figure imgf000178_0001
Figure imgf000179_0001
Figure imgf000180_0001
Figure imgf000181_0001
Figure imgf000182_0001
LC method used
Method A
Autopurification System from Waters: 2767 sample Manager, 2489 UV/Visible Detector, 2545 Quaternary Gradient Module.
Column: Phenomenex Synergi C18 Reversed Phase, 4 pm particle size, 80 A, 75 x 30.00 mm,
100 mg of product dissolve in DMF injected
DAD Wavelength (nm): 220 and 254
Solvent Gradient: A = water (Fluka Analytical)
B= Acetonitrile for prep. HPLC (Fluka Analytical)
Time A% B% Flow (mL/min)
0.00 90.0 10.0 50.00
0.01 90.0 10.0 50.00
6.00 60.0 40.0 50.00
7.90 60.0 40.0 50.00
8.00 0.0 100.0 50.00
8.90 0.0 100.0 50.00
9.00 90.0 10.0 50.00
9.50 90.0 10.0 50.00
9.55 90.0 10.0 50.00
LC-MS methods used
Method ZMD
ZMD Mass Spectrometer from Waters (Single quadrupole mass spectrometer) Instrument Parameter:
Ionisation method: Electrospray
Polarity: positive ions
Capillary (kV) 3.80, Cone (V), Extractor (V) 3.00, Source Temperature (°C) 150, Desolvation Temperature (°C) 350, Cone Gas Flow (L/Hr) OFF, Desolvation Gas Flow (L/Hr) 600
Mass range: 100 to 900 Da
HP 1100 HPLC from Agilent: solvent degasser, binary pump, heated column compartment and diode-array detector.
Column: Phenomenex Gemini C18, 3 mm particle size, 110 A 30 x 3 mm,
Temp: 60 °C
DAD Wavelength range (nm): 200 to 500
Solvent Gradient:
A = water + 0.05 % HCOOH
B= Acetonitrile/Methanol (4: 1, v:v) + 0.04 % HCOOH
Time A% B% Flow (mL/min)
0.00 95.0 5.0 1.700
2.00 0.0 100.0 1.700 2.80 0.0 100.0 1.700
2.90 95.0 5.0 1.700
3.00 95.0 5.0 1.700 Method ZCQ
ZQ Mass Spectrometer from Waters (Single quadrupole mass spectrometer)
Instrument Parameter:
Ionisation method: Electrospray
Polarity: positive ions
Capillary (kV) 3.00, Cone (V) 30.00, Extractor (V) 2.00, Source Temperature (°C) 100, Desolvation Temperature (°C) 250, Cone Gas Flow (L/Hr) 50, Desolvation Gas Flow (L/Hr) 400
Mass range: 100 to 900 Da
HP 1100 HPLC from Agilent: solvent degasser, quaternary pump (ZCQ) / binary pump (ZDQ), heated column compartment and diode-array detector.
Column: Phenomenex Gemini C18, 3 mm particle size, 110 A, 30 x 3 mm,
Temp: 60 °C
DAD Wavelength range (nm): 200 to 500
Solvent Gradient:
A = water + 0.05 % HCOOH
B= Acetonitrile/Methanol (4: 1, v:v) + 0.04 % HCOOH
Time A% B% Flow (mL/min)
0.00 95.0 5.0 1.700
2.00 0.0 100.0 1.700
2.80 0.0 100.0 1.700
2.90 95.0 5.0 1.700
3.00 95.0 5.0 1.700
Method UPLC
ACQUITY SQD Mass Spectrometer from Waters (Single quadrupole mass spectrometer) Ionisation method: Electrospray
Polarity: positive ions
Capillary (kV) 3.80, Cone (V) 20.00, Extractor (V) 3.00, Source Temperature (°C) 150, Desolvation Temperature (°C) 400, Cone Gas Flow (L/Hr) 60, Desolvation Gas Flow (L/Hr) 700
Mass range: 100 to 800 Da Column: Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1.8 micron; Temperature: 60°C
DAD Wavelength range (nm): 210 to 400
Solvent Gradient:
5 A = water/methanol 9: 1, 0.1 % HCOOH
B= Acetonitrile+ 0.1 % HCOOH
Time A% B% Flow (mL/min)
0.00 100.0 0.0 0.75
2.50 0.0 100.0 0.75
10 2.80 0.0 100.0 0.75
3.00 100.0 0.0 0.75
UPLC1
ACQUITY SQD Mass Spectrometer from Waters (Single quadrupole mass spectrometer) 15 Instrument Parameters:
Ionisation method: Electrospray
Polarity: positive ions
Capillary (kV) 3.00, Cone (V) 20.00, Extractor (V) 3.00, Source Temperature (°C) 150, Desolvation Temperature (°C) 400, Cone Gas Flow (L/Hr) 60, Desolvation Gas Flow (L/Hr) 20 700
Mass range: 100 to 800 Da
Type of column: Waters ACQUITY UPLC HSS T3; 1.8 micron particle size, 30 mm x 2.1 mm;
Temperature: 60°C
25 DAD Wavelength range (nm): 210 to 400
Solvent Gradient:
A: Water/Methanol 9: 1 + 0.1% formic acid
B: Acetonitrile + 0.1% formic acid
Time A% B% Flow (mL/min)
30 0.00 100.0 0.0 1.700
2.50 0.0 100.0 1.700
2.80 0.0 100.0 1.700
3.00 100.0 0.0 1.700
35 OA_2min_30V
SQD Mass Spectrometer from Waters (Single quadrupole mass spectrometer): Ionization method: Electrospray; Polarity: positive and negative ions; Capillary (kV): 3.00; Cone (V): 30.00; Extractor (V): 2.00; Source Temperature (°C): 150; Desolvation Temperature (°C): 250; Cone Gas Flow (L/Hr): 0; Desolvation Gas Flow (L/Hr): 650; Mass range: 100 to 900 Da
Acquity UPLC from Waters:
Binary pump, heated column compartment and diode-array detector; Solvent degasser, binary pump, heated column compartment and diode-array detector; Column: Phenomenex Gemini C18, 3 - m, 30 x 2 mm; Temp: 60 °C; DAD Wavelength range (nm): 210 to 500
Solvent Gradient:
A = H20 + 5% MeOH + 0.05 % HCOOH
B= Acetonitril + 0.05 % HCOOH
Time A% B% Flow (mL/min)
0.00 100 0 0.850
1.20 0 100 0.850
1.50 0 100 0.850
OA_2min_45V
SQD Mass Spectrometer from Waters (Single quadrupole mass spectrometer):
Ionization method: Electrospray; Polarity: positive and negative ions; Capillary (kV):
3.00; Cone (V): 45.00; Extractor (V): 2.00 ; Source Temperature (°C): 150; Desolvation Temperature (°C): 250; Cone Gas Flow (L/Hr): 0; Desolvation Gas Flow (L/Hr): 650; Mass range: 100 to 900 Da
Acquity UPLC from Waters:
Binary pump, heated column compartment and diode-array detector; Solvent degasser, binary pump, heated column compartment and diode-array detector; Column: Phenomenex Gemini C18, 3 - m, 30 x 2 mm; Temp: 60°C; DAD Wavelength range (nm): 210 to 500
Solvent Gradient:
A = H20 + 5% MeOH + 0.05 % HCOOH
B= Acetonitril + 0.05 % HCOOH
Time A% B% Flow (mL/min)
0.00 100 0 0.850
1.20 0 100 0.850
1.50 0 100 0.850 OA_3min_30V
ZQ Mass Spectrometer from Waters (Single quadrupole mass spectrometer):
Ionization method: Electrospray; Polarity: positive and negative ions; Capillary (kV): 3.00; Cone (V): 30.00; .Extractor (V): 2.00; Source Temperature (°C): 100; Desolvation Temperature (°C): 250; Cone Gas Flow (L/Hr): 50; Desolvation Gas Flow (L/Hr): 400; Mass range: 100 to 900 Da
HP 1100 HPLC from Agilent:
Solvent degasser, binary pump, heated column compartment and diode-array detector; Column: Phenomenex Gemini C18, 3 - m, 30 x 3 mm; Temp: 60°C; DAD
Wavelength range (nm): 210 to 500;
Solvent Gradient:
A = water + 5% MeOH + 0.05 % HCOOH
B= Acetonitrile + 0.05 % HCOOH
Time A% B% Flow (mL/min)
0.00 100 0 1.700
2.00 0 100 1.700
2.80 0 100 1.700
2.90 100 0 1.700
3.00 100 0 1.700
OA_5min_45V
SQD Mass Spectrometer from Waters (Single quadrupole mass spectrometer) Ionization method: Electrospray; Polarity: positive and negative ions; Capillary (kV):
3.00; Cone (V): 45.00; Extractor (V): 2.00; Source Temperature (°C): 150; Desolvation Temperature (°C): 250; Cone Gas Flow (L/Hr): 0; Desolvation Gas Flow (L/Hr): 650; Mass range: 100 to 900 Da
Acquity UPLC from Waters:
Binary pump, heated column compartment and diode-array detector; Solvent degasser, binary pump, heated column compartment and diode-array detector; Column: Phenomenex Gemini C18, 3 - m, 30 x 2 mm; Temp: 60°C; DAD Wavelength range (nm): 210 to 500
Solvent Gradient:
A = water + 5% MeOH + 0.05 % HCOOH
B= Acetonitrile + 0.05 % HCOOH
Time A% B% Flow (mL/min)
0.00 100 0 0.850 3.40 0 100 0.850
4.10 0 100 0.850
4.20 100 0 0.850
4.60 100 0 0.850
5
OA_8min_Pol_30V
ZQ Mass Spectrometer from Waters (Single quadrupole mass spectrometer) Ionization method: Electrospray; Polarity: positive and negative ions; Capillary (kV): 3.00; Cone (V): 30.00; .Extractor (V): 2.00; Source Temperature (°C): 100; Desolvation 10 Temperature (°C): 250; Cone Gas Flow (L/Hr): 50; Desolvation Gas Flow (L/Hr): 400; Mass range: 100 to 900 Da
HP 1100 HPLC from Agilent:
Solvent degasser, binary pump, heated column compartment and diode-array detector; Column: HyperCarb, 3 - m, 30 x 3 mm; Temp: 60°C; DAD Wavelength range (nm): 15 210 to 500
Solvent Gradient:
A = water + 5% MeOH + 0.05 % HCOOH
B= Acetonitrile + 0.05 % HCOOH
Time A% B% Flow (mL/min)
0.00 100 0 1.700
6.00 0 100 1.700
7.70 0 100 1.700
7.80 100 0 1.700
8.00 100 0 1.700
25
Method U
ACQUITY SQD Mass Spectrometer from Waters (Single quadrupole mass spectrometer) Ionisation method: Electrospray
Polarity: positive ions
30 Capillary (kV) 3.80, Cone (V) 20.00, Extractor (V) 3.00, Source Temperature (°C) 150, Desolvation Temperature (°C) 400, Cone Gas Flow (L/Hr) 60, Desolvation Gas Flow (L/Hr) 700
Mass range: 100 to 800 Da
Column: Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of 35 column: 2.1 mm; Particle Size: 1.8 micron; Temperature: 60°C
DAD Wavelength range (nm): 210 to 400 Solvent Gradient:
A = water/methanol 9: 1, 0.1 % HCOOH
B= Acetonitrile+ 0.1 % HCOOH
Time A% B% Flow (mL/min)
0 100.0 0.0 0.75
2.5 0.0 100.0 0.75
2.8 0.0 100.0 0.75
3.00 100.0 0.0 0.75 Biological examples:
Puccinia recondita f. sp. tritici I wheat / leaf disc preventative (Brown rust):
Wheat leaf segments cultivated variety (cv) Kanzler were placed on agar in 24-well plates and sprayed with formulated test compound diluted in water at an application rate of 200ppm. The leaf disks were inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf segments were incubated at 19°C and 75% relative humidity under a light regime of 12/12 h (light/dark) in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (7 - 9 days after application). The following compounds gave at least 80% control of Puccinia recondita f. sp. tritici. P.12, P.01, P.09, P.24, P.03, P.04, P.14, P.22, P.08, P.10, P.55, P.58, P.69, P.72, P.88, P.91, P.92, P.94, P.97, P.100, P.102, P.103
Puccinia recondita f. sp. tritici I wheat / leaf disc curative fBrown rust):
Wheat leaf segments cv Kanzler were placed on agar in 24-well plates. The leaf segments were inoculated with a spore suspension of the fungus. The plates were stored in darkness at 19°C and 75% relative humidity. The formulated test compound diluted in water was applied at an application rate of 200ppm 1 day after inoculation. The leaf segments were incubated at 19°C and 75% relative humidity under a light regime of 12/12 h
(light/dark) in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (6 - 8 days after application). The following compounds gave at least 80% control of Puccinia recondita f. sp. tritici.?. 2, P.01, P.09, P.02, P.24, P.03, P.04, P.22, P.08, P.19, P.10, P.12, P.55, P.56, P.58, P.62, P.69, P.72, P.88, P.92, P.94, P.97, P.100, P.102, P.103 Phaeosphaeria nodorum (Septoria nodorum) /wheat / leaf disc preventative (Glume blotchO:
Wheat leaf segments cv Kanzler were placed on agar in a 24-well plate and sprayed with formulated test compound diluted in water at an application rate of 200ppm. The leaf disks are inoculated with a spore suspension of the fungus 2 days after application. The inoculated test leaf disks are incubated at 20°C and 75% relative humidity under a light regime of 12/12 h (light/dark) in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application). The following compounds gave at least 80% control of Phaeosphaeria nodorum: P.12, P.Ol, P.09, P.02, P.24, P.03, P.04, P.13, P.14, P.20, P.22, P.08, P.19, P.10, P.24, P.51, P.12, P.10, P.46, P.55, P.56, P.57, P.58, P.61, P.63A, P.69, P.72, P.74, P.76, P.82, P.84, P.88, P.91, P.92, P.94, P.95, P.96, P.97, P.98, P.100, P.102, P.103 Pyrenophora teres I barley / leaf disc preventative (Net blotch):
Barley leaf segments cv Hasso are placed on agar in a 24-well plate and sprayed with formulated test compound diluted in water at an application rate of 200ppm. The leaf segments are inoculated with a spore suspension of the fungus two days after application of the test solution. The inoculated leaf segments are incubated at 20°C and 65% relative humidity under a light regime of 12/12 h (light/dark) in a climate cabinet and the activity of a compound is assessed as disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 - 7 days after application). The following compounds gave at least 80% control of Pyrenophora teres. P.12, P.Ol, P.09, P.24, P.03, P.04, P.13, P.14, P.20, P.22, P.15, P.08, P.19, P.23A, P.10, P.55, P.58, P.72, P.74, P.76, P.82, P.83, P.84, P.88, P.92, P.94, P.95, P.96, P.97, P.98, P.100, P.103
Botrvotinia fuckeliana (Botrvtis cinerea) I liquid culture (Gray mould):
Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (Vogels broth). After placing a DMSO solution of test compound into a 96-well microtiter plate at an application rate of 200ppm, the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 3-4 days after application. The following compounds gave at least 80% control of Botryotinia fuckeliana: P.12, P.11, P.Ol, P.09, P.02, P.24, P.03, P.04, P.20, P.17, P.18, P.22, P.15, P.08, P.19, P.21, P.23A, P.10, P.34, P.33, P.24, P.56, P.51, P.50, P.12, P.47, P.46, P.45, P.39, P.38, P. 35, P.29, P.55, P.56, P.57, P.58, P.61, P.62, P.63B, P.64, P.65, P.66, P.67, P.69, P.71, P.72, P.74, P.75, P.76, P.77, P.79, P.80, P.82, P.83, P.84, P.85, P.86, P.87, P.88, P.89, P.90; P.91, P.92, P.94, P.95, P.96, P.97, P.98, P.99, P.100, P.101, P.102, P.103, P.104
Glomerella laaenarium ( Colletotrichum laaenariuni) I liquid culture (Anthracnose) : 5 Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a DMSO solution of test compound into a 96-well microtiter plate at an application rate of 200ppm, the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth is measured photometrically 3-4 days after application. The following compounds gave at least 10 80% control of Glomerella lagena um: P.12, P.Ol, P.09, P.24, P.03, P.04, P.22, P.10, P.24, P.51, P.12, P.55, P.56, P.57, P.58, P.63A, P.63B, P.69, P.72, P.76, P.82, P.83, P.84, P.88, P.90; P.91, P.92, P.94, P.95, P.96, P.97, P.98, P.99, P.100, P.102, P.103
Mvcosphaerella arachidis (Cercospora arachidicola) I liquid culture (early leaf spot): 15 Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a DMSO solution of test compound into a 96-well microtiter plate at an application rate of 200ppm, the nutrient broth containing the fungal spores was added. The test plates are incubated at 24°C and the inhibition of growth was determined photometrically 4-5 days after application. The following compounds gave at 20 least 80% control of Mycosphaerella arachidis. P.12, P.Ol, P.09, P.02, P.24, P.03, P.04, P.13, P.14, P.20, P.18, P.22, P.15, P.08, P.19, P.23A, P.10, P.33, P.24, P.56, P.55, P.51, P.50, P.49, P.12, P.47, P.46, P.45, P.39, P.38, P.35, P.29, P.55, P.56, P.57, P.58, P.60, P.61, P.62, P.66, P.67, P.68, P.69, P.74, P.75, P.76, P.77, P.78, P.79, P.80, P.82, P.83, P.84, P.86, P.87, P.88, P.89, P.90; P.91, P.92, P.94, P.95, P.96, P.97, P.98, P.99, P.100, P.101, P.102, P.103, 25 P.104, P.107, P.108
Mvcosphaerella graminicola (Septoria tritici) I liquid culture (Septoria blotch):
Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a DMSO solution of test compound into a 96-well
30 microtiter plate at an application rate of 200ppm, the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 4-5 days after application. The following compounds gave at least 80% control of Mycosphaerella graminicola: P.12, P.11, P.Ol, P.09, P.02, P.24, P.03, P.04, P.05, P.13, P.14, P.20, P.16, P.22, P.15, P.08, P.19, P.23A, P.10, P.34, P.33, P.56,
35 P.51, P.50, P.12, P.47, P.46, P.45, P.39, P.38, P.35, P.29, P.55, P.56, P.57, P.58, P.61, P.62, P.63A, P.67, P.68, P.69, P.72, P.74, P.75, P.76, P.77, P.78, P.80, P.82, P.83, P.84, P.85, P.87, P.88, P.89, P.90; P.91, P.92, P.94, P.95, P.96, P.97, P.98, P.99, P.100, P.101, P.102, P.103, P.104
Gaeumannomyces graminis I liquid culture (Take-all of cereals'):
Mycelial fragments of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a DMSO solution of test compound into a 96-well microtiter plate at an application rate of 200ppm, the nutrient broth Cp.33, containing the fungal spores is added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 4-5 days after application. The following compounds gave at least 80% control of Gaeumannomyces graminis. P.12, P.02, P.04, P.13, P.14, P.22, P.23A, P.10, P.24, P.56, P.55, P.54, P.53, P.51, P.12, P.46, P.37, P.35, P.55, P.57, P.58, P.61, P.69, P.74, P.76, P.83, P.84, P.94, P.95, P.96, P.100, P.102, P.103, P.105
Thanatephorus cucumeris (Rhizoctonia solani) I liquid culture (foot rot, dampinq- off):
Mycelia fragments of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a DMSO solution of the test compounds into a 96-well microtiter plate at an application rate of 200ppm, the nutrient broth containing the fungal material was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 3-4 days after application. The following compounds gave at least 80% control of Thanatephorus cucumeris. P.12, P.24, P.03, P.04, P.19, P.10, P.51, P.56, P.58, P.62, P.69, P.82, P.88, P.91, P.92, P.94, P.95, P.96, P.100 Monoaraohella nivalis ( Microdochium nivale) I liquid culture ffoot rot cereals):
Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a DMSO solution of test compound into a 96-well microtiter plate at an application rate of 200ppm, the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 4-5 days after application. The following compounds gave at least 80% control of Monographella nivalis. P.12, P.09, P.02, P.24, P.03, P.04, P.05, P.22, P.08, P.10, P.24, P.51, P.38, P.35, P.55, P.56, P.57, P.58, P.69, P.74, P.76, P.78, P.80, P.82, P.88, P.91, P.92, P.94, P.95, P.96, P.97, P.98, P.99, P.100, P.103 Blumeria graminis f. SP. tritici ' (Ervsiphe graminis f. sp. tritici)! wheat / leaf disc preventative (Powdery mildew on wheat): Wheat leaf segments cv. Kanzler were placed on agar in a 24-well plate and sprayed with the formulated test compound diluted in water at an application rate of 200ppm. The leaf disks were inoculated by shaking powdery mildew infected plants above the test plates 1 day after application. The inoculated leaf disks were incubated at 20°C and 60% relative humidity under a light regime of 24 h darkness followed by 12h/12h (dark/light) in a climate chamber and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check leaf segments (6 - 8 days after application). The following compounds gave at least 80% control of Blumeria graminis. P.12, P.01, P.09, P.24, P.03, P.04, P.22, P.08, P.23A, P.10, P.12, P.55, P.56, P.58, P.69, P.72, P.74, P.82, P.83, P.84, P.88, P.91, P.92, P.94, P.96, P.97, P.100, P.102, P.103
Alternaria solan i 7 tomato / leaf disc (early blight):
Tomato leaf disks cultivated variety (cv.) Baby were placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water at an application rate of 200ppm. The leaf disks were inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf disks were incubated at 23°C/21°C (day/night) and 80% relative humidity under a light regime of 12/12 h (light/dark) in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check disk leaf disks (5 - 7 days after application). The following compounds gave at least 80% control of Alternaria solani: P.58, P.94
Maanaoorthe arisea (Pyricularia orvzae) I rice / leaf disc preventative (Rice Blast): Rice leaf segments cv. Ballila were placed on agar in multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water at an application rate of 200ppm. The leaf segments were inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf segments were incubated at 22°C and 80% rh under a light regime of 24 h darkness followed by 12/12 h (light/dark) in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 - 7 days after application). The following compounds gave at least 80% control of Magnaporthe grisea: P.62, P.72, P.74, P.76, P.82, P.88, P.91, P.92, P.94, P.96, P.97, P.100, P.101

Claims

Claims:
1. A compound of formula (I):
Figure imgf000194_0001
wherein
R1 represents hydrogen, halogen, CN, SH, d-C8 alkylthio, d-C8 alkylsulphinyl, d-C8 alkylsulphonyl, NH2, CrCi0 alkyi, C3-C8 cycloalkyi, C2-C8 alkenyl, C2-C8 alkynyl,
(R80)carbonyl(d-C4 alkyi), phenyl or pyridyl, wherein the alkyi, cycloalkyi, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, NH-CrC8 alkyi, N(CrC8 alkyl)2, N02, OR8, CrC4 alkyi, CrC4 haloalkyl, C3-C6 cycloalkyi and a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms;
R2 represents hydrogen, d-C8 alkyi, C3-C8 cycloalkyi, C3-C8 alkenyl, C3-C8 alkynyl, benzyl, phenyl or pyridyl, wherein the alkyi, cycloalkyi, alkenyl, alkynyl, phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, CrC4 alkyi, CrC4 haloalkyl, CrC4 alkoxy and CrC4 haloalkoxy;
D1 represents N or C-Y1;
D2 represents N or C-Y2;
wherein both D1 and D2 cannot be N;
A represents group A-1, A-2, or A-3:
Figure imgf000194_0002
A-1 A-2 A-3
Wherein A1 represents the cycle Ala, Al , or Alc:
Figure imgf000195_0001
» 1c
R3 represents hydrogen, halogen, CN, SH, d-C8 alkylthio, CrC8 alkylsulphinyl, d-C8 alkylsulphonyl, NH2, CrCi0 alkyl, C3-C8 cycloalkyl, C2-C8 alkenyl, C2-C8 alkynyl,
(R80)carbonyl(d-C4 alkyl), phenyl or pyridyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, NH-CrC8 alkyl, N(CrC8 alkyl)2, N02, OR8, CrC4 alkyl, CrC4 haloalkyl, C3-C6 cycloalkyl and a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms;
R4, R5, R6 and R7 independently of one another represent hydrogen, halogen, CN,
N02, d-C8 alkyl, C3-C8 cycloalkyl, C2-C8 alkenyl, C2-C8 alkynyl, phenyl, a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, COR9, OR8, SH, d-C8-alkylthio, d-C8- alkylsulphinyl, d-C8-a I kyl sulphonyl, phenylthio, phenylsulphinyl, phenylsulphonyl, N(R10)2, C02R8, 0(CO)R9, CON(R10)2, NR10COR9 or CR9N-OR8, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, phenyl and heterocycle are optionally substituted by one or more groups
independently selected from halogen, CN, NH2, N02, OR8, d-C4 alkyl and d-C4 haloalkyl; or, when A is A-l, wherein A1 is Ala or Al , or when A is A-2, R5 and R6, R6 and R4, or R7 and R4 together with the fragment of the ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a partially or fully unsaturated 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from O, S, N and N(R10), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, and wherein the ring formed by R5 and R6, R6 and R4, or R7 and R4 is optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, d-C4 alkyl, d-C4 haloalkyl, d-C4 alkoxy and d-C4 haloalkoxy;
G1 and G2 independently of one another represent -C(R12R13)-;
G3 represents -C(R12R13)-, O, N(R14) or S;
or G1 and G2, or G2 and G3, or G1 and G1 together represent -CR12=CR13-;
each R12 and R13 independently of one another represent hydrogen, halogen, Ci-C4 alkyl, Ci-C4 haloalkyl, Ci-C4 alkoxy or d-C4 haloalkoxy; R represents hydrogen, OH, d-d alkyl, d-d alkoxy, C3-C6 cycloalkyl, d-d alkylcarbonyl or d- haloalkylcarbonyl;
p represents 0, 1 or 2;
X represents X-2, X-3, X-4 or X-5:
#—∑—∑—# #— Z— Z— Z— # #— Z— Z— Z— Z— #
X-2 X-3 X-4
#_z!o_z _z!2_ z!3_z!i_#
X
Z1, Z2, Z3, Z5, Z6, Z7, Z8, Z9, Z10, Z11, Z13 and Z14 independently of one another represent CR15R16, C=0 or C=CR17R18;
Z4 and Z12 represent CR19R20, SiR21R22, C=0 or C=CR17R18;
each R15 and R16 independently of one another represent hydrogen, halogen, CN, OH, Crd alkyl, Cr haloalkyi or phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, Crd alkyl, Crd haloalkyi, Crd alkoxy and Crd haloalkoxy;
or R15 and R16 together with the carbon atom to which they are attached may form a C3-C6 cycloalkyl group or a C3-C6 halocycloalkyl group;
each R17 and R18 independently of one another represent hydrogen, halogen, Crd alkyl or Crd haloalkyi;
each R19, R20, R21 and R22 independently of one another represent hydrogen, halogen, CN, OH, Ci-d alkyl, Ci-d haloalkyi or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, Crd alkyl, Crd haloalkyi, Crd alkoxy and Crd haloalkoxy;
or R19 and R20 together with the carbon atom to which they are attached may form a C3-C6 cycloalkyl group or a C3-C6 halocycloalkyl group;
wherein the groupings X-2, X-3, X-4 and X-5 contain at most one ring which contains either only one of the radicals Z1 to Z14 or two radicals Z1 to Z14 or three radicals Z1 to Z14 or four radicals Z1 to Z14 as ring members; wherein radicals Z1, Z3, Z6 and Z10 are not substituted by OH; and wherein none of Z1, Z2, Z3, Z4, Z5, Z6, Z7, Z8, Z9, Z10, Z11, Z12, Z13 and Z14 represent a carbon atom substituted by two OH;
Y1, Y2 and Y3 independently of one another represent hydrogen, halogen, CN, N02, d-C8 alkyl, C3-C8 cycloalkyl, C2-C8 alkenyl, C2-C8 alkynyl, phenyl, a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, COR9, OR8, SH, Crd-alkylthio, d-C8- alkylsulphinyl, Ci-C8-alkylsulphonyl, phenylthio, phenylsulphinyl, phenyl sulphonyl, N(R °)2, C02R8, 0(CO)R9, CON(R10)2, NR10COR9 or CR9N-OR8, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, phenyl, and heterocycle are optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OR8, d-d alkyl and d-d haloalkyl; or Y1 and Y3, or Y2 and Y3 together with the fragment of the pyridyl ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a partially or fully unsaturated 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from O, S, N and N(R10), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, and wherein the ring formed by Y1 and Y3, or Y2 and Y3 is optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, d-d alkyl, Crd haloalkyl, Crd alkoxy and Crd haloalkoxy;
each R8 independently of one another represents hydrogen, d-C8 alkyl, C3-C8 cycloalkyl, C3-C8 alkenyl, C3-C8 alkynyl, phenyl, benzyl or a 5- or 6-membered heterocycle containing one to three heteroatoms independently selected from O, S and N, providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, phenyl, benzyl and heterocycle are optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, CrC alkyl, CrC -haloalkyl, CrC alkoxy, CrC haloalkoxy and Crd-alkoxy-Crd-alkyl;
each R9 independently of one another represents hydrogen, d-C8 alkyl, C3-C8 cycloalkyl, C2-C8 alkenyl, C2-C8 alkynyl, phenyl, benzyl or pyridyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, Crd alkyl, Crd haloalkyl, Crd alkoxy and d-C4 haloalkoxy;
each R10 independently of one another represents hydrogen, OH, d-C8 alkyl, d-C8 alkoxy, CrC8-alkoxy-CrC4-alkyl, C3-C8 alkenyl, C3-C8 alkynyl, or COR9, wherein the alkyl, alkoxy, alkenyl and alkynyl are optionally substituted by one or more halogen;
wherein when two radicals R10 are attached to the same nitrogen atom, these radicals can be identical or different;
wherein when two radicals R10 are attached to the same nitrogen atom, both of these radicals cannot be OH, Crd alkoxy or Crd haloalkoxy;
and wherein when two radicals R10 are attached to the same nitrogen atom, these two radicals together with the nitrogen atom to which they are attached may form a cycle B- 1, B-2, B-3, B-4, B-5, B-6, B-7 or B-8:
Figure imgf000198_0001
B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 wherein the cycle formed is optionally substituted by one or more groups
independently selected from halogen, CN, NH2, N02, OH, Ci-C4 alkyl, Ci-C4 haloalkyl, Ci-C4 alkoxy and Ci-C4 haloalkoxy;
or a salt or an N-oxide thereof.
2. A compound according to claim 1, wherein
R1 represents hydrogen, Ci-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, phenyl, pyridyl or (R80)carbonyl(Ci-C4 alkyl), wherein the alkyl, alkenyl, alkynyl, cycloalkyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, OR8, NH2, NH-Ci-C8 alkyl, N(CrC8 alkyl)2, d-C alkyl, d-C haloalkyl, C3-C6 cycloalkyl and pyridyl;
R2 represents hydrogen, Ci-C8 alkyl, Ci-C8 haloalkyl, C3-C8 cycloalkyl, C3-C8 halocycloalkyl, C3-C8 alkenyl, C3-C8 haloalkenyl, C3-C8 alkynyl, C3-C8 haloalkynyl, benzyl or pyridyl, wherein the benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, d-C4 alkyl, CrC4 haloalkyl, d-C4 alkoxy and CrC4 haloalkoxy;
R3 represents hydrogen, d-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, phenyl, pyridyl or (R80)carbonyl(d-C4 alkyl), wherein the alkyl, alkenyl, alkynyl, cycloalkyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, OR8, NH2, NH-CrC8 alkyl, N(CrC8 alkyl)2, CrC4 alkyl, CrC4 haloalkyl, C3-C6 cycloalkyl and pyridyl;
A represents group A-l, A-2 or A-3;
R4, R5, R6 and R7 independently of one another represent hydrogen, halogen, CN, OR8, Ci-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyl, phenyl, pyridyl, N(R10)2, C02R8, NR10COR9, SH, d-C8-alkylthio, Ci-C8-alkylsulphinyl, d-C8-alkylsulphonyl, phenylthio, phenylsulphinyl or phenylsulphonyl, wherein the alkyl, alkenyl, cycloalkyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, OR8, d-C4 alkyl and d-C4 haloalkyl;
or, when A is A-l, wherein A1 is Ala or Al , or when A is A-2, R5 and R6, R6 and R4, or
R4 and R7, together with the fragment of the ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a partially or fully unsaturated 5- to 7-membered heterocyclic ring containing one to three heteroatoms independently selected from O, S, N and N(R10), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, wherein the ring formed by R5 and R6, R6 and R4, or R4 and R7 is optionally
substituted by one or more groups independently selected from halogen, CN, Ci-C4 alkyl, d- C4 haloalkyi, Ci-C4 alkoxy and Ci-C4 haloalkoxy;
X represents X-3 or X-5;
Z3, Z5, Z10, Z11, Z13 and Z14 independently of one another represent CR15R16 or C=CR17R18;
Z4 and Z12 represent CR19R20 or C=CR17R18;
each R15 and R16 independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl or CrC4 haloalkyi;
each R17 and R18 independently of one another represent hydrogen, halogen, d-C4 alkyl or d-C4 haloalkyi;
each R19 and R20 independently of one another represent hydrogen, halogen, CN, OH, CrC4 alkyl, CrC4 haloalkyi or phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
or R19 and R20 together with the carbon atom to which they are attached may form a
C3-C6 cycloalkyi group or a C3-C6 halocycloalkyl group;
Y1, Y2 and Y3 independently of one another represent hydrogen, halogen, CN, OR8,
Ci-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyi, phenyl, pyridyl, N(R10)2, C02R8, NR10COR9, SH, Q-
C8-alkylthio, CrC8-alkylsulphinyl, d-C8-alkylsulphonyl, phenylthio, phenylsulphinyl or phenylsulphonyl, wherein the alkyl, alkenyl, cycloalkyi, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, OR8, d-C4 alkyl and d-C4 haloalkyi;
each R8 independently of one another represents hydrogen, d-C8 alkyl, d-C8 haloalkyi, C3-C8 alkenyl, C3-C8 haloalkenyl, C3-C8 haloalkynyl, phenyl, benzyl or pyridyl, wherein the phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, d-C4 alkyl, d-C4-haloalkyl, d-C4 alkoxy and d-C4 haloalkoxy;
each R9 independently of one another represents hydrogen, d-C8 alkyl or d-C8 haloalkyi;
each R10 independently of one another represents hydrogen, d-C8 alkyl or COR9; wherein when two radicals R are attached to the same nitrogen atom, these radicals can be identical or different;
and wherein when two radicals R10 are attached to the same nitrogen atom, these two radicals together with the nitrogen atom to which they are attached may form a cycle B- 1, B-2, B-3, B-4 or B-5 wherein the cycle formed is optionally substituted by one or more groups independently selected from halogen, methyl and halomethyl.
3. A compound according to claim 1, wherein
R1 represents hydrogen, d-d alkyl, C2-d alkenyl, phenyl or pyridyl, wherein the alkyl, alkenyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, OH, NH2, NH-Crd alkyl, N(d-C4 alkyl)2, d-C alkyl, d-C4 haloalkyl, d-C4 alkoxy, Crd haloalkoxy and C3-C6 cycloalkyl;
R2 represents d-C4 alkyl, C3-C6 alkenyl, C3-C6 alkynyl or benzyl, wherein the alkyl, alkenyl, alkynyl and benzyl are optionally substituted by one or more groups independently selected from halogen, CN, Crd alkoxy and Crd haloalkoxy;
R3 represents hydrogen, Crd alkyl, C2-C4 alkenyl, phenyl or pyridyl, wherein the alkyl, alkenyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, OH, NH2, NH-CrC alkyl, N(CrC alkyl)2, CrC alkyl, Crd haloalkyl, Crd alkoxy, Crd haloalkoxy and C3-C6 cycloalkyl;
A represents group A-l, A-2 or A-3;
R4, R5, R6 and R7 independently of one another represent hydrogen, halogen, OR8, CN, d-d alkyl, C3-C6 cycloalkyl, N(R10)2, phenyl, C02R8 or NR10COR9, wherein the alkyl, cycloalkyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, Crd alkyl, CrC4-haloalkyl, Crd alkoxy and Crd haloalkoxy; or, when A is A-l, wherein A1 is Ala or Al , or when A is A-2, R5 and R6, R6 and R4, or
R4 and R7, together with the fragment of the pyridyl ring to which they are attached may form a fully or partially unsaturated 5- or 6-membered carbocyclic ring, optionally substituted by one or more groups independently selected from halogen, methyl and halomethyl;
X represents X-3;
Z3 and Z5 independently of one another represent CR15R16 or C=CR17R18;
Z4 represents CR19R20 or C=CR17R18;
each R15 and R16 independently of one another represent hydrogen, halogen, CN, OH, d-d alkyl or CrC haloalkyl;
each R17 and R18 independently of one another represent hydrogen, halogen, Crd alkyl or Crd haloalkyl; each R and R independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl, C1-C4 haloalkyi or phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
or R19 and R20 together with the carbon atom to which they are attached may form a
C3-C6 cycloalkyl group or a C3-C6 halocycloalkyl group;
wherein at least two of Z3, Z4 and Z5 are methylene;
Y1, Y2 and Y3 independently of one another represent hydrogen, halogen, OR8, CN, C1-C4 alkyl, C3-C6 cycloalkyl, N(R10)2, phenyl, C02R8 or NR10COR9 wherein the alkyl, cycloalkyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, C1-C4 alkyl, Ci-Crhaloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy;
each R8 independently of one another represents hydrogen, d-C8 alkyl, CrC8 haloalkyi, C3-C8 alkenyl, C3-C8 haloalkenyl, C3-C8 alkynyl, C3-C8 haloalkynyl, phenyl, benzyl, or pyridyl, wherein the phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, d-C4 alkyl, Q-Crhaloalkyl, d-C4 alkoxy and C1-C4 haloalkoxy;
each R9 independently of one another represents hydrogen, d-C4 alkyl or d-C4 haloalkyi;
each R10 independently of one another represents hydrogen or d-C4 alkyl;
wherein when two radicals R10 are attached to the same nitrogen atom, these radicals can be identical or different;
and wherein when two radicals R10 are attached to the same nitrogen atom, these two radicals together with the nitrogen atom to which they are attached may form a cycle B- 1, B-2, B-3, B-4 or B-5 wherein the cycle formed is optionally substituted by one or more groups independently selected from halogen, methyl and halomethyl.
4. A compound according to anyone of claims 1-3, wherein
R1 represents hydrogen, C1-C4 alkyl, C1-C4 haloalkyi, phenyl or pyridin-2-yl, wherein the phenyl and pyridin-2-yl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
R2 represents hydrogen, d-C8 alkyl, or d-C8 haloalkyi;
R3 represents hydrogen, Crd alkyl, d-C4 haloalkyi, phenyl or pyridin-2-yl, wherein the phenyl and pyridin-2-yl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
A represents group A-l, A-2, or A-3; R4, R5, R6 and R7 independently of one another represent hydrogen, halogen, OH, CN, C1-C4 alkyl, C1-C4 alkoxy, C3-C6 alkenyloxy, C3-C6 cycloalkyi, N(R10)2, phenyl or C02R8, wherein the alkyl, alkoxy, alkenyloxy, cycloalkyi and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, C1-C4 alkyl, Ci-C4-haloalkyl, Ci-C4 alkoxy and Ci-C4 haloalkoxy;
X represents X-3;
Z3 and Z5 independently of one another represent CR15R16 or C=CR17R18;
Z4 represents CR19R20 or C=CR17R18;
each R15 and R16 independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl or CrC haloalkyl;
each R17 and R18 independently of one another represent hydrogen, halogen, methyl or halomethyl;
each R19 and R20 independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl, CrC4 haloalkyl or phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
or R19 and R20 together with the carbon atom to which they are attached may form a C3-C6 cycloalkyi group or a C3-C6 halocycloalkyl group;
wherein at least two of Z3, Z4 and Z5 are methylene;
Y1, Y2, and Y3 independently of one another represent hydrogen, halogen, OH, CN,
C1-C4 alkyl, Q-C, alkoxy, C3-C6 alkenyloxy, C3-C6 cycloalkyi, N(R10)2, phenyl or C02R8, wherein the alkyl, alkoxy, alkenyloxy, cycloalkyi and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, d-C4 alkyl, CrC4-haloalkyl, d-C4 alkoxy and C1-C4 haloalkoxy;
each R8 independently or one another represents hydrogen, d-C4 alkyl or d-C4 haloalkyl;
each R10 independently of one another represents hydrogen or d-C4 alkyl;
wherein when two radicals R10 are attached to the same nitrogen atom, these radicals can be identical or different;
and wherein when two radicals R11 are attached to the same nitrogen atom, these two radicals together with the nitrogen atom to which they are attached may form a cycle B- 1, B-2, B-3, B-4 or B-5, wherein the cycle formed is optionally substituted by one or more groups independently selected from halogen, methyl and halomethyl.
5. A compound according to any one of claims 1 to 3, wherein R3 represents C1-C4 alkyl, C2-C4 alkenyl, phenyl or pyridyl, wherein the alkyl, alkenyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, Ci-C4 alkoxy and C1-C4 haloalkoxy.
5
6. A compound according to any one of claims 1 to 5, wherein A represents A-l wherein A1 is Ala or wherein A represents A-2.
7. A compound according to any one claims 1 to 6, wherein R4, R5, R6 and R7
10 independently of one another represent hydrogen, Ci-C4 alkyl, CN or Ci-C4 alkoxy, wherein the alkyl and alkoxy are optionally substituted by one or more groups independently selected from halogen, CN, d-C4 alkoxy and CrC4 haloalkoxy.
8. A compound according to any one of claims 1, 2 and 5 to 7, wherein X represents X-3 15 or X-5.
9. A compound according to any one of claims 1, 2 and 5 to 8, wherein X represents X- 3.
20 10. A compound according to any one of claims 1 to 9, wherein
X represents X-3;
Z3 and Z5 represent methylene;
Z4 represents CR19R20 or C=CR17R18;
each R17 and R18 independently of one another represent hydrogen, halogen, methyl 25 or halomethyl;.
each R19 and R20 independently of one another represent hydrogen, halogen, CN, OH, CrC4 alkyl, CrC4 haloalkyl or phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
30 or R19 and R20 together with the carbon atom to which they are attached may form a
C3-C6 cycloalkyl group optionally substituted by halogen.
11. A compound according to any one of claims 1 to 3 and 5 to 10, wherein R1 represents CrC4 alkyl, C2-C4 alkenyl, phenyl or pyridyl, wherein the alkyl, alkenyl, phenyl and pyridyl are 35 optionally substituted by one or more groups independently selected from halogen, CN, d-C4 alkoxy and CrC4 haloalkoxy.
12. A compound according to any one of claims 1 to 11, wherein G1, G2 and G3 represent C(R3 )2, wherein each R34 independently of one another represents hydrogen or Ci-C4 alkyi.
13. A compound according to any one of claims 1 to 12, wherein p is 1.
14. A compound according to any one of claims 1 and 5 to 13, wherein R5 and R6, R6 and R4, or R4 and R7 together with the fragment of the pyridyl ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a 5- to 7- membered heterocyclic ring containing one to three heteroatoms independently selected from O, S, N and N(R5), providing that the heterocycle does not contain adjacent oxygen atoms, adjacent sulphur atoms, or adjacent sulphur and oxygen atoms, and wherein the ring formed by R5 and R6, R6 and R4, or R4 and R7 is optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, d-C4 alkyi, CrC4 haloalkyl, d-C4 alkoxy and CrC4 haloalkoxy.
15. A compound according to any one of claims 1-3 and 5 to 14, wherein R5 and R6, R6 and R4, or R4 and R7, together with the fragment of the pyridyl ring to which they are attached may form a fully or partially unsaturated 6-membered carbocyclic ring optionally substituted by one or more groups independently selected from halogen, methyl and halomethyl.
16. A compound according to claim 1 wherein
R1 represents hydrogen, d-C4 alkyi, CrC4 haloalkyl and phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
R2 represents hydrogen, d-C4 alkyi, C3-C6 alkenyl or C3-C6 alkynyl, wherein the alkyi, alkenyl, or alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, d-C4 alkoxy and d-C4 haloalkoxy;
D1 represents C-Y1;
D2 represents C-Y2;
A represents group A-l, A-2, or A-3;
A1 represents the cycle Ala, Al , or Alc;
R3 represents hydrogen, CN, d-C4 alkyi, C3-C6 cycloalkyi, C2-C4 alkenyl, C2-C4 alkynyl, (CrC4alkoxy)carbonyl(d-C4 alkyi), phenyl or pyridyl, wherein the alkyi, cycloalkyi, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, NH-Ci-C8 alkyl, N(Ci-C8 alkyl)2, N02, OH, d-C4 alkyl, Ci-C4 haloalkyl, C3-C6 cycloalkyi and pyridyl or pyrroline;
R4 represents hydrogen, halogen, CN, d-C6 alkyl, C3-C6 cycloalkyi, C2-C6 alkenyl, C2- C6 alkynyl, phenyl, OH, CrC4 alkoxy, NH2, NH(Ci-C4 alkyl), N(Ci-C4 alkyl)2, CO(Ci-C4 alkyl), wherein the alkyl, cycloalkyi, alkenyl, alkynyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
R5 represents hydrogen, halogen, CN, Ci-C8 alkyl, C3-C6 cycloalkyi, C2-C8 alkenyl, C2- C8 alkynyl, phenyl, pyridyl, CO(Ci-C4 alkyl), OH, d-C4 alkoxy, NH2, NH(Ci-C4 alkyl), N(Ci-C4 alkyl)2 or C02(Ci-C4 alkyl), wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, OR8, Ci-C4 alkyl, Q-C4 haloalkyl;
R6 represents hydrogen, halogen, CN, Ci-C4 alkyl, C3-C6 cycloalkyi, C2-C6 alkenyl, C2- C6 alkynyl, phenyl, d-C4 alkoxy or benzyloxy, wherein the alkyl, cycloalkyi, alkenyl, alkynyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
or R5 and R6 together with the fragment of the ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a partially or fully unsaturated 5- to 7-membered heterocyclic ring containing one heteroatom independently selected from O, S, N NH and N(d-C4 alkyl), wherein the ring formed is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
R7 represents hydrogen, halogen, CN, Q-C4 alkyl, C3-C6 cycloalkyi, C2-C4 alkenyl, C2- C4 alkynyl, OH, Q-C4 alkoxy, NH2, NH(Q-C4 alkyl), N(Q-C4 alkyl)2, C02(CrC4 alkyl) and C02(CrC4 alkyl), wherein the alkyl, cycloalkyi, alkenyl and alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
G1 and G2 independently of one another represent -C(R12R13)-;
G3 represents -C(R12R13)-, O, N(R14) or S;
each R12 and R13 independently of one another represent hydrogen, halogen, d-C4 alkyl, CrC4 haloalkyl, d-C4 alkoxy or d-C4 haloalkoxy;
R14 represents hydrogen, OH, d-C4 alkyl, d-C4 alkoxy, C3-C6 cycloalkyi, d-C8 alkylcarbonyl or d-C8 haloalkylcarbonyl;
p represents 1 or 2;
X represents X-3;
Z3 and Z5 independently of one another represent CR15R16 or C=CR17R18; Z4 represent CR19R20;
each R15 and R16 independently of one another represent hydrogen, halogen, Ci-C4 alkyl or Ci-C4 haloalkyl;
each R17 and R18 independently of one another represent hydrogen, halogen, methyl or halomethyl;
each R19, R20 independently of one another represent hydrogen, halogen, CN, OH, Ci-C alkyl or Ci-C haloalkyl;
or R19 and R20 together with the carbon atom to which they are attached may form a C3-C5 cycloalkyi group or a C3-C6 halocycloalkyl group;
Y1 and Y2 each represent H;
Y3 represents hydrogen, halogen, CN, Ci-C4 alkyl, C3-C6 cycloalkyi, C2-C6 alkenyl, C2-C6 alkynyl or d-C4 alkoxy wherein the alkyl, cycloalkyi, alkenyl and alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, C1-C4 alkyl and Q-C, haloalkyl;
each R8 independently of one another represents hydrogen, d-C8 alkyl, C3-C8 cycloalkyi, C3-C8 alkenyl, C3-C8 alkynyl, phenyl, benzyl or pyridyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl, phenyl, benzyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, N02, OH, d-C4 alkyl, d-C4- haloalkyl, d-C4 alkoxy, CrC4 haloalkoxy and CrC4-alkoxy-CrC4-alkyl.
17. A compound according to claim 16 wherein
R1 represents hydrogen, d-C4 alkyl, d-C4 haloalkyl and phenyl, wherein the phenyl is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
R2 represents hydrogen, d-C4 alkyl, C3-C6 alkenyl or C3-C6 alkynyl, wherein the alkyl, alkenyl, or alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
D1 represents C-Y1;
D2 represents C-Y2;
A represents group A-l, A-2, or A-3;
A1 represents the cycle Ala, Al , or Alc;
R3 represents hydrogen, CN, d-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl or phenyl, wherein the alkyl, cycloalkyi, alkenyl, alkynyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, NH-d-C4 alkyl, N(d-C4 alkyl)2, OH, d-C4 alkyl, d-C4 haloalkyl, C3-C6 cycloalkyi, pyridyl or pyrroline; R4 represents hydrogen, halogen, CN, d-C6 alkyl, C3-C6 cycloalkyl, C2-C4 alkenyl, C2- C4 alkynyl, phenyl, Ci-C4 alkoxy or CO(Ci-C4 alkyl), wherein the alkyl, cycloalkyl, alkenyl, alkynyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
R5 represents hydrogen, halogen, CN, Ci-C8 alkyl, C3-C6 cycloalkyl, C2-C8 alkenyl, C2-
C8 alkynyl, phenyl, pyridyl, CO(CrC alkyl), OH, d-C alkoxy, NH2, NH(d-C alkyl), N(CrC alkyl)2 or C02(Ci-C4 alkyl), wherein the alkyl, cycloalkyl, alkenyl, alkynyl, phenyl and pyridyl are optionally substituted by one or more groups independently selected from halogen, CN, NH2, OR8, Ci-C alkyl, d-C haloalkyl;
R6 represents hydrogen, halogen, CN, Ci-C4 alkyl, Ci-C4 alkoxy or benzyloxy, wherein the alkyl and phenyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
or R5 and R6 together with the fragment of the ring to which they are attached may form a partially or fully unsaturated 5- to 7-membered carbocyclic ring or a partially or fully unsaturated 5- to 7-membered heterocyclic ring containing one heteroatom independently selected from O or S, wherein the ring formed is optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
R7 represents hydrogen, halogen, CN, Q-C4 alkyl, C3-C6 cycloalkyl, C2-C4 alkenyl, C2- C4 alkynyl, OH, Q-C4 alkoxy, NH2, NH(Q-C4 alkyl), N(Q-C4 alkyl)2, C02(CrC4 alkyl) and C02(CrC4 alkyl), wherein the alkyl, cycloalkyl, alkenyl and alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, methyl, halomethyl, methoxy and halomethoxy;
G1 represents -CH2-;
G2 represents -C(R12R13)-;
G3 represents -C(R12R13)-, O, N(R14) or S;
each R12 and R13 independently of one another represent hydrogen or d-C4 alkyl; R14 represents hydrogen or d-C4 alkyl;
p represents 1 or 2;
X represents X-3;
Z3 and Z5 independently of one another represent CR15R16 or C=CR17R18;
Z4 represent CR19R20;
each R15 and R16 independently of one another represent hydrogen, halogen, d-C4 alkyl or d-C4 haloalkyl;
each R17 and R18 independently of one another represent hydrogen, halogen, methyl or halomethyl; each R , R independently of one another represent hydrogen, halogen, CN, OH, C1-C4 alkyl or Ci-C haloalkyl;
or R19 and R20 together with the carbon atom to which they are attached may form a C3-C5 cycloalkyl group or a C3-C6 halocycloalkyl group;
wherein the grouping X-3 contains at most one ring which contains either only one of the radicals Z3 to Z5 or two radicals Z3 to Z5 or three radicals Z3 to Z5 as ring members;
Y1 and Y2 each represent H;
Y3 represents hydrogen, methyl, methoxy, methoxymethyl, wherein the methyl, methoxy, methoxymethyl are optionally substituted by one or more halogen;
each R8 independently of one another represents hydrogen, C1-C5 alkyl, C3-C6 alkenyl,
C3-C4 alkynyl, phenyl or benzyl.
18. A compound of formula (II)
Figure imgf000208_0001
wherein D1, D2, X, Y3, R1 and R2 are as defined for a compound of formula (I) in any one of claims 1 to 17; or a salt or N-oxide thereof;
or a compound of formula (III)
Figure imgf000208_0002
wherein T1 and T2 independently of one another represent Ci-C8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-Ci-C6-alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C6 alkyl;
D1, D2, A, X, Y3 and R1 are as defined for a compound of formula (I) in any one of claims 1 to 17; or a salt or N-oxide thereof;
or a compound of formula (IV)
Figure imgf000209_0001
wherein X' represents X'-l, X'-2 or X'-3
#— z— # #—∑—∑—# #—z—z—z—#
X'-1 X'-2 X'-3
wherein D1, D2, A, Z3, Z6, Z7, Z10, Z11, Z12, Y3, R1 and R2 are as defined for a compound of formula (I) in any one of claims 1 to 16; or a salt or N-oxide thereof;
or a compound of formula (V)
Figure imgf000209_0002
wherein X' represents X'-l, X'-2 or X'-3
#— z— # #—∑—∑—# #—z—z—z—#
X'-1 X'-2 X'-3
T1 and T2 independently of one another represent CrC8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC6-alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C6 alkyl;
D1, D2, A, Z3, Z6, Z7, Z10, Z11, Z12, Y3 and R1 are as defined for a compound of formula (I) in any one of claims 1 to 17; or a salt or N-oxide thereof;
or a compound of formula (VI)
Figure imgf000209_0003
wherein X' represents X'-l, X'-2 or X'-3
#— z— # #—∑—∑—# #—z—z—z—#
X'-1 X'-2 X'-3
R23 and R24 independently of one another represent hydrogen, halogen, CN, Ci-C4 alkyl, Ci-C4 haloalkyi or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, d-C4 alkyl, CrC4 haloalkyi, d-C4 alkoxy and CrC4 haloalkoxy;
D1, D2, A, Z3, Z6, Z7, Z10, Z11, Z12, Y3, R1 and R2 are as defined for a compound of formula (I) in any one of claims 1 to 17; or a salt or N-oxide thereof;
or a compound of formula
Figure imgf000210_0001
(VII)
wherein X' represents X'-l, X'-2 or X'-3
#— z— # #—∑—∑—# #—z—z—z—#
X'-1 X'-2 X'-3
R23 and R24 independently of one another represent hydrogen, halogen, CN, Ci-C4 alkyl, Ci-C4 haloalkyi or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, d-C4 alkyl, CrC4 haloalkyi, d-C4 alkoxy and CrC4 haloalkoxy;
T1 and T2 independently of one another represent d-C8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC6-alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C6 alkyl;
D1, D2, A, Z3, Z6, Z7, Z10, Z11, Z12, Y3 and R1 are as defined for a compound of formula (I) in any one of claims 1 to 17; or a salt or N-oxide thereof;
or a compound of formula (VIII)
Figure imgf000211_0001
wherein X' represents X'-l, X'-2 or X'-3
#— z— # #—∑—∑—# #—z—z—z—#
X'-1 X'-2 X'-3
D1, D2, Z3, Z6, Z7, Z10, Z11, Z12, Y3, R1 and R2 are as defined for a compound of formula (I) in any one of claims 1 to 17; or a salt or N-oxide thereof;
or a compound of formula (IX)
Figure imgf000211_0002
wherein X' represents X'-l, X'-2 or X'-3
#— z— # #—∑—∑—# #—z—z—z—#
X'-1 X'-2 X'-3
D1, D2, Z3, Z6, Z7, Z10, Z11, Z12, Y3, R1 and R2 are as defined for a compound of formula (I) in any one of claims 1 to 17; or a salt or N-oxide thereof;
or a compound of formula (X)
Figure imgf000211_0003
wherein X' represents X'-l, X'-2 or X'-3
#— z— # #— z— z— # #— z— z— z— #
X'-1 X'-2 X'-3 D1, D2, Z3, Z6, Z7, Z10, Z11, Z12, Y3, R1 and R2 are as defined for a compound of formula (I) in any one of claims 1 to 17; or a salt or N-oxide thereof;
or a compound of formula (XI)
Figure imgf000212_0001
wherein R is a halogen or a sulfonic acid ester group;
T1 and T2 independently of one another represent CrC8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC6-alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C6 alkyl;
X' represents X'-l, X'-2 or X'-3
#— z— # #—∑—∑—# #—z—z—z—#
X'-1 X'-2 X'-3
D1, D2, Z3, Z6, Z7, Z10, Z11, Z12, Y3 and R1 are as defined for a compound of formula (I) in any one of claims 1 to 17; or a salt or N-oxide thereof;
or a compound of formula (XII)
Figure imgf000212_0002
(XII)
wherein X' represents X'-l, X'-2 or X'-3
#— z— # #—∑—∑—# #—z—z—z—#
X'-1 X'-2 X'-3
A, Z3, Z6, Z7, Z10, Z11 and Z12 are as defined for a compound of formula (I) in any one of claims 1 to 17; or a salt or N-oxide thereof;
or a compound of formula
Figure imgf000212_0003
(XIII)
wherein X' represents X'-l, X'-2 or X'-3 #—∑—# #—∑—∑—# #—∑—∑—∑—#
X'-1 X'-2 Χ'-3
Τ1 and Τ2 independently of one another represent CrC8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC6-alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C6 alkyl;
D1, D2, Z3, Z6, Z7, Z10, Z11, Z12, Y3 and R1 are as defined for a compound of formula (I) in any one of claims 1 to 17; or a salt or N-oxide thereof;
or a compound of formula (XV)
Figure imgf000213_0001
(XV)
wherein R25 is a halogen or a sulfonic acid ester group;
X' represents X'-l, X'-2 or X'-3
#—∑—# #—∑—∑—# #—∑—∑—∑—#
X'-1 X'-2 X'-3
R^ and independently of one another represent hydrogen, halogen, CN, Ci-C4 alkyl, Ci-C4 haloalkyi or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, d-C4 alkyl, CrC4 haloalkyi, d-C4 alkoxy and CrC4 haloalkoxy;
T1 and T2 independently of one another represent CrC8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC6-alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C6 alkyl;
D1, D2, Z3, Z6, Z7, Z10, Z11, Z12, Y3 and R1 are as defined for a compound of formula (I) in any one of claims 1 to 17; or a salt or N-oxide thereof
or a compound of formula (XVI)
Figure imgf000214_0001
(XVI)
wherin R24 represents hydrogen, halogen, CN, Ci-C4 alkyl, Q- haloalkyl or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, d-C4 alkyl, d-C4 haloalkyl, d-C4 alkoxy and CrC4 haloalkoxy;
T1 and T2 independently of one another represent CrC8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC6-alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C6 alkyl;
D1, D2, Y3 and R1 are as defined for a compound of formula (I) in any one of claims 1 to 17; or a salt or N-oxide thereof;
or a compound of formula (XVIII)
Figure imgf000214_0002
(XVIII)
wherein R23 and R24 independently of one another represent hydrogen, halogen, CN, Ci-C4 alkyl, Ci-C4 haloalkyl or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, Ci-C4 alkyl, Ci-C4 haloalkyl, Ci-C4 alkoxy and Ci-C4 haloalkoxy;
T1 and T2 independently of one another represent d-C8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-Ci-C6-alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C6 alkyl;
D1, D2, Y3 and R1 are as defined for a compound of formula (I) in any one of claims 1 to 17; or a salt or N-oxide thereof;
or a compound of formula (XIX)
Figure imgf000215_0001
wherein R represents CrC4 alkyl;
R23 and R24 independently of one another represent hydrogen, halogen, CN, Q-C4 alkyl, Ci-C4 haloalkyi or phenyl, wherein phenyl is optionally substituted by one or more groups independently selected from halogen, CN, d-C4 alkyl, CrC4 haloalkyi, d-C4 alkoxy and CrC4 haloalkoxy;
T1 and T2 independently of one another represent CrC8 alkoxy, or T1 and T2 together with the carbon they are attached to form a carbonyl group or an acetal or ketal function of the form C(0-CrC6-alkylidene-0), wherein the alkylidene fragment is optionally substituted by one to four d-C6 alkyl;
D1, D2, Y3 and R1 are as defined for a compound of formula (I) in any one of claims 1 to 17; or a salt or N-oxide thereof.
19. A compound of formula (XI) according to claim 18, wherein R25 represents chlorine, bromine, iodine, mesylate, tosylate, triflate, phenylsulfonic acid ester, nitro-phenylsulfonic acid ester, or nonafluorobutylsulfonic acid ester;
or a compound of formula (XV) according to claim 17 wherein R25 represents chlorine, bromine, iodine, mesylate, tosylate, triflate, phenylsulfonic acid ester, nitro-phenylsulfonic acid ester, or nonafluorobutylsulfonic acid ester.
20. A fungicidal composition comprising a fungicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 17, optionally comprising an additional active ingredient.
21. A method of controlling or preventing phytopathogenic diseases on useful plants or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a fungicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 17.
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