WO2016087593A1 - Nouvelles quinolinylamidines fongicides - Google Patents

Nouvelles quinolinylamidines fongicides Download PDF

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Publication number
WO2016087593A1
WO2016087593A1 PCT/EP2015/078542 EP2015078542W WO2016087593A1 WO 2016087593 A1 WO2016087593 A1 WO 2016087593A1 EP 2015078542 W EP2015078542 W EP 2015078542W WO 2016087593 A1 WO2016087593 A1 WO 2016087593A1
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methyl
alkyl
ethyl
butyl
phenyl
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PCT/EP2015/078542
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Olivier Jacob
Sarah Sulzer-Mosse
Fredrik Emil Malcolm Cederbaum
Thomas James Hoffman
Werner Zambach
Matthias Weiss
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Syngenta Participations Ag
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
    • C07D215/38—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07D401/02—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to novel microbiocidal, in particular fungicidal, quinolinylamidine compounds.
  • 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.
  • the present invention relates to compounds of formula (I)
  • R and R 2 independently of each other represent hydrogen, Ci-C 4 alkyl, Ci-C 4 fluoroalkyl or C 3 - C 6 cycloalkyl; or
  • R and R 2 together with the nitrogen atom to which they are attached form a three to six- membered saturated cyclic group which optionally contains either one oxygen atom or one sulphur atom;
  • R 3 represents hydrogen, halogen, cyano, hydroxy, formyl, carboxy, amino, Ci-C 4 alkyl, C 2 - C 5 alkenyl, C 2 -C 5 alkynl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy or C 3 -C 6 cycloalkyl;
  • R 4 represents hydrogen, halogen, cyano, hydroxy, formyl, carboxy, amino, Ci-C 4 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynl, d-C 6 haloalkyl, d-C 6 alkoxy or C 3 -C 6 cycloalkyl;
  • R 5 represents R 9 -(Z) m -;
  • R 6 , R 7 ,R 8 independently of each other represent hydrogen, halogen, cyano, hydroxy, formyl, carboxy, amino, Ci-C 4 alkyl, C 2 -C 5 alkenyl, C 2 -C 5 alkynl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy or d- C 4 haloalkoxy;
  • n 0, 1 or 2;
  • Z represents Ci-C 4 alkyl, wherein the alkyl is optionally substituted by one or more groups independently selected from halogen, CN, OH, Ci-C 4 alkylcarbonyl, Ci-C 4 alkoxycarbonyl, d- C 4 -haloalkyl, CN, Ci-C 4 -alkoxy and Ci-C 4 -haloalkoxy;
  • R 9 represents hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, wherein the alkyl, alkenyl, alkynyl and cycloalkoxyare optionally substituted by one or more groups independently selected from halogen, hydroxyl, cyano, N0 2 , OH, SH, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynl, d-C 6 haloalkyl, d-C 6 alkoxy, C 3 -C 8 cycloalkyl C 3 -C 8 cycloalkoxy, formyl, C 2 -C 6 alkylcarbonyl, Ci-C 6 alkylthio, Ci-C 6 alkylsulfinyl and Ci-C 6 alkylsulfonyl; or
  • R 9 represents D-A-Ci-C 6 alkyl-, D-A-Ci-C 6 alkyl-, D-A-C C 6 alkyl-, D-A-Ci-C 6 alkyl-, D-A-d- C 6 alkyl-, D-A-Ci-C 6 alkyl-, D-A-C 2 -C 6 alkenyl-, D-A-C 2 -C 6 alkenyl-, D-A-C 2 -C 6 alkenyl-, D-A-C 2 -C 6 alkenyl-, D-A-C 2 -C 6 alkenyl- , D-A-C 2 -C 6 alkenyl- , D-A-C 2 -C 6 alkenyl-, D-A-C 2 -C 6 alkenyl-, D-A-C 2 -C 6 alkenyl-, D-A-C 2 -C 6 alkynyl-, D-A-C 2
  • R 9 represents NHR 4 ;
  • D represents d-dalkyl, d-dalkenyl, d-dalkynyl, d-dcycloalkyl, benzyl, phenyl each of which are optionally substituted by one or more groups independently selected from halogen, cyano, hydroxy, mercapto, d-dhaloalkyl, d-dalkoxy, formyl, C 2 -C 5 alkylcarbonyl, d-dalkoxycarbonyl, d- dalkylthio, d-dhaloalkylthio, d-dalkylsulfinyl and d-dalkylsulfonyl;
  • each R 2 and R 3 independently of each other represents hydrogen, formyl, d-dalkyl, d- dhaloalkyl, d-dalkylcarbonyl, d-dalkoxycarbonyl, benzyl or phenyl; or
  • R 2 and R 3 together with the nitrogen atom to which they are attached form a three to six- membered saturated cyclic group which optionally contains either one oxygen atom or one sulphur atom;
  • R 4 represents phenyl optionally substituted by fluoro, CN , OH, methyl, ethyl, n-propyl, iso- propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 -CH 3 , CF 2 -CF 3 , OMe, OEt, OiPr, OPr, OCHF 2 and OCF 3 ;
  • each R 5 independently represents hydrogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, C 3 -C 5 alkenyl, C 3 - C 5 haloalkenyl, C 3 -C 5 alkynyl, C 3 -C 6 cycloalkyl, benzyl or phenyl wherein the alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, cycloalkyl, benzyl and phenyl are optionally substituted by one or more groups independently selected from halogen, cyano, hydroxy, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy and d- C 4 haloalkoxy;
  • Substituents at a nitrogen atom are always different from halogen.
  • a hydroxy, mercapto or amino substituent is not to be placed on an ocarbon relative to a heteroatom of a core fragment.
  • Halogen either as a lone substituent or in combination with another substituent (e.g. haloalkyl) 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, n- propyl, n-butyl, n-pentyl, n-hexyl, / ' so-propyl, sec-butyl, / ' so-butyl, ieri-butyl, neo-pentyl, n-heptyl or 1 ,3- dimethylbutyl, and usually methyl or ethyl.
  • alkenyl and alkynyl groups can be mono- or di-unsatu rated and examples thereof are derived from the above mentioned alkyl groups.
  • the alkenyl group is an unsaturated straight or branched chain having a carbon-carbon double bond and, depending on the number of carbon atoms it contains, is, for example ethenyl, 1 -propenyl, 2-propenyl, 1 -methyl-ethenyl, 1 -butenyl, 2-butenyl, 3-butenyl, 1 -methyl-1 -propenyl, 2-methyl-1 - propenyl, 2-methyl-2-propenyl, 1 -pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1 -methyl-1 -butenyl, 2- methyl-1 -butenyl, 3-methyl-1 -butenyl, 1 -methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1 -methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1 , 1 -dimethyl-2-
  • the alkynyl group is an unsaturated straight or branched chain having a carbon-carbon triple bond and, depending on the number of carbon atoms it contains, is, for example ethynyl, 1 -propynyl, 2-propynyl, 1 -butynyl, 2-butynyl, 3-butynyl, 1 -methyl-2-propynyl, 1 -pentynyl, 2-pentynyl, 3-pentynyl, 4- pentynyl, 3-methyl-1 -butynyl, 1 -methyl-2-butynyl, 1 -methyl-3-butynyl, 2-methyl-3-butynyl, 1 , 1 -dimethyl- 2-propynyl, 1 -ethyl-2-propynyl, 1 -hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexyny
  • 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, trifluoromethyl, monochloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2,2-difluoroethyl, 2-fluoroethyl, 1 , 1-difluoroethyl, 1-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 , 1-difluoro-2,2,2-trichloroethyl, 2,2,3,3- tetrafluoroethyl and 2,2,2-trichloroethyl, and typically trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.
  • Alkoxy is, for example, methoxy, ethoxy, propoxy, / ' so-propoxy, n-butoxy, / ' so-butoxy, sec-butoxy and ieri-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, n-butylthio, iso- butylthio, sec-butylthio or ieri-butylthio, and usually methylthio or ethylthio.
  • Alkylsulphonyl is, for example, methylsulphonyl, ethylsulphonyl, propylsulphonyl, iso- propylsulphonyl, n-butylsulphonyl, / ' so-butylsulphonyl, sec-butylsulphonyl or ieri-butylsulphonyl, and usually methylsulphonyl or ethylsulphonyl.
  • Alkylsulphinyl is, for example, methylsulphinyl, ethylsulphinyl, propylsulphinyl, iso- propylsulphinyl, n-butylsulphinyl, / ' so-butylsulphinyl, sec-butylsulphinyl or ieri-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, n- propoxymethyl, n-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.
  • monocyclic groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, and thiadiazolyl.
  • 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.
  • No heterocycle contains adjacent oxygen atoms, adjacent sulphur atoms, or adjacent oxygen and sulphur atoms.
  • a moiety is indicated as being (optionally) substituted, e.g. alkyl, this includes those moieties where they are part of a larger group, e.g. the alkyl 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, cycloalkyl, preferably there are no more than two such substituents, more preferably no more than one such substituent.
  • R and R 2 independently of each other represent hydrogen, Ci-C 4 alkyl, Ci-C 4 fluoroalkyl or C 3 - C 6 cycloalkyl; or
  • R and R 2 together with the nitrogen atom to which they are attached form a three to six- membered saturated cyclic group which optionally contains either one oxygen atom or one sulphur atom.
  • R and R 2 independently of each other represent hydrogen, Ci-C 4 alkyl or cyclopropyl.
  • R and R 2 independently of each other represent hydrogen, methyl, ethyl, isopropyl, n-propyl or cyclopropyl.
  • R and R 2 independently of each other represent methyl or ethyl.
  • R represents methyl and R 2 represents ethyl.
  • R represents methyl and R 2 is as defined above.
  • R 3 represents hydrogen, halogen, cyano, hydroxy, formyl, carboxy, amino, C 1 -C4 alkyl, C 2 - C 5 alkenyl, C 2 -C 5 alkynl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy or C 3 -C 6 cycloalkyl.
  • R 3 represents hydrogen, chloro, methyl or ethyl.
  • R 3 represents methyl.
  • R 4 represents hydrogen, halogen, cyano, hydroxy, formyl, carboxy, amino, Ci-C 4 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynl, d-C 6 haloalkyl, d-C 6 alkoxy or C 3 -C 6 cycloalkyl.
  • R 4 represents hydrogen, halogen, cyano, hydroxy, Ci-C 4 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynl, d-C 6 haloalkyl or d-C 6 alkoxy.
  • R 4 represents hydrogen, halogen, cyano, hydroxy, d-d alkyl or d-C 6 haloalkyl.
  • R 4 represents hydrogen
  • R 5 represents R 9 -(Z) m -.
  • n 0, 1 or 2.
  • m represents 0 or 1 .
  • Z represents methylene or ethylene, each of which is optionally substituted by one or more methyl groups.
  • Z represents Ci-C 4 alkyl, wherein the alkyl is optionally substituted by one or more groups independently selected from halogen, CN, OH, Ci-C 4 alkylcarbonyl, Ci-C 4 alkoxycarbonyl, d- C 4 -haloalkyl, CN , Ci-C 4 -alkoxy and Ci-C 4 -haloalkoxy.
  • Z represents methlyene or ethylene, wherein the methlyene and ethylene are optionally substituted by one or more groups independently selected from fluorine, CN, OH, methyl, ethyl, propyl, iso-propyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 -CF 3 , CN, OMe, OEt, COMe, COEt, COiPr, COtBu, C0 2 Me, C0 2 Et, C0 2 iPr, and C0 2 tBu.
  • R 9 represents d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, wherein the alkyl, alkenyl, alkynyl and cycloalkoxyare optionally substituted by one or more groups independently selected from halogen, hydroxyl, cyano, N0 2 , OH, SH, Ci-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynl, Ci-C 6 haloalkyl, Ci-C 6 alkoxy, C 3 -C 8 cycloalkyl C 3 -C 8 cycloalkoxy, formyl, C 2 -C 6 alkylcarbonyl, d-C 6 alkylthio, d-C 6 alkylsulfinyl and d-C 6 alkylsulfonyl; or
  • R 9 represents D-A-d-C 6 alkyl-, D-A-d-C 6 alkyl-, D-A-C C 6 alkyl-, D-A-d-C 6 alkyl-, D-A-C C 6 alkyl-, D-A-d-C 6 alkyl-, D-A-C 2 -C 6 alkenyl-, D-A-C 2 -C 6 alkenyl-, D-A-C 2 -C 6 alkenyl-, D-A-C 2 -C 6 alkenyl- , D-A-C 2 -C 6 alkenyl- , D-A-C 2 -C 6 alkenyl-, D-A-C 2 -C 6 alkenyl-, D-A-C 2 -C 6 alkenyl-, D-A-C 2 -C 6 alkynyl-, D-A-C 2 -C 6 alkynyl-, D-A-C 2 -C 6 al
  • R 9 represents NHR 4 .
  • R 9 represents hydrogen, d-C 6 alkyl, d-C 6 alkenyl or d-C 6 alkynyl wherein the alkyl, alkenyl and alkynyl are optionally be optionally substituted by one or more groups independently selected from halogen, CN, OH, d-C 4 alkyl, C 2 -C 4 alkenyl, d-C 4 fluoroalkyl, d-C 4 alkoxy, and C 2 - C 5 alkylcarbonyl; or
  • R 9 represents a five- or six-membered saturated or partially saturated monocyclic system which contains one or two members selected from the group consisting of N, N(R 11 ), O and S, optionally substituted by one or more groups independently selected from the group consisting of halogen, CN, N0 2 , OH, SH, CHO, d-C 4 alkyl, d-C 4 haloalkyl, C 3 -C 6 cycloalkyl, C 2 -C 5 alkenyl, C 2 -C 5 alkynyl, C 2 - C 5 haloalkynyl, Ci-C 4 alkoxy, Ci-C 4 haloalkoxy, C 3 -C 5 alkynyloxy, Ci-C 4 alkylcarbonyl and Ci-C 4 alkoxycarbonyl; or
  • R 9 represents a C 3 -C 8 carbocyclic system, which may be partially saturated or fully saturated and is optionally substituted by one or more groups independently selected from halogen, CN, N0 2 , OH, SH, CHO, COOH, d-C 4 alkyl, d-C 4 alkoxy, d-C 4 haloalkyl, d-C 4 haloalkoxy, C 3 -C 6 cycloalkyl and d-C 4 alkylcarbonyl; or
  • R 9 represents NHR 14 ;
  • R 9 represents hydrogen, d-C 6 alkyl, d-C 6 alkenyl or d-C 6 alkynyl, wherein the alkyl, alkenyl and alkynyl are optionally substituted by one or more groups selected from chloro, fluoro, bromo, CN, OH, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 -CH 3 , CF 2 -CF 3 , OMe, OEt, OiPr, OPr, OCHF 2 , and OCF 3 ; or
  • R 9 represents a five- or six-membered saturated monocyclic system which contains one or two members selected from the group consisting of N, N(R 11 ), O and S, optionally substituted by one or more groups independently selected from chloro, fluoro, bromo, CN, N0 2 , OH, SH, CHO, Ci-C 4 alkyl, Ci-C 4 fluoroalkyl, d-C 4 alkoxy, Ci-C 4 fluoroalkoxy, Ci-C 4 alkylcarbonyl and Ci-C 4 alkoxycarbonyl; or
  • R 9 represents a five- or six-membered aromatic monocyclic system which contains one or two members selected from the group consisting of N, N(R 16 ), O and S, optionally substituted by one or more groups independently selected from chloro, fluoro, bromo, CN, N0 2 , OH, SH, CHO, Ci-C 4 alkyl, Ci-C 4 fluoroalkyl, Ci-C 4 alkoxy, Ci-C 4 fluoroalkoxy, Ci-C 4 alkylcarbonyl, and Ci-C 4 alkoxycarbonyl; or
  • R 9 represents a five or six membered carbocyclic system which can be partially saturated or fully saturated and is optionally substituted by one or more groups independently selected from chloro, fluoro, bromo, CN, N0 2 , OH, SH, Ci-C 4 alkyl, Ci-C 4 alkoxy, Ci-C 4 fluoroalkyl and Ci-C 4 fluoroalkoxy; or R 9 represents NHR 4 .
  • R 9 represents hydrogen, d-C 6 alkyl, d-C 6 alkenyl or d-C 6 alkynyl, wherein the alkyl, alkenyl and alkynyl are optionally substituted by one or more groups selected from fluoro, CN, OH, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CH 2 F, CHF 2 , CF 3 , CHF- CH 3 , CF 2 -CH 3 , CF 2 -CH 3 , CF 2 -CF 3 , OMe, OEt, OiPr, OPr; or
  • R 9 represents a five- or six-membered saturated monocyclic system which contains one or two members selected from the group consisting of N, N(R 11 ), O and S, optionally substituted by one or more groups independently selected from chloro, fluoro, bromo, CN, N0 2 , OH , SH , methyl, ethyl, n- propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 - CH 3 , CF 2 -CF 3 , OMe, OEt, OiPr, OnPr, OCHF 2 and OCF 3 ; or
  • R 9 represents a five- or six-membered aromatic monocyclic system which contains one or two members selected from the group consisting of N, N(R 16 ), O and S, optionally substituted by one or more groups independently selected from fluoro, CN, N0 2 , OH, SH, CHO, methyl, ethyl, n-propyl, iso- propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 -CH 3 , CF 2 -CF 3 , OMe, OEt, OiPr, OPr, OCHF 2 , OCF 3 , SCHF 2 , SCF 3 , COMe, COEt, COiPr, COtBu, C0 2 Me, C0 2 Et, C0 2 iPr, and C0 2 t
  • R 9 represents a five or six membered carbocyclic system which can be partially saturated or fully saturated and is optionally substituted by one or more groups independently selected from fluoro, CN, N0 2 , OH, SH, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 -CH 3 , CF 2 -CF 3 , OMe, OEt, OiPr, OPr, OCHF 2 and OCF 3 ; or
  • R 9 represents NHR 4 .
  • R 0 represents hydrogen, formyl, Ci-C 4 alkyl, Ci-C 4 haloalkyl, C 3 -C 5 alkenyl or C 2 -C 5 alkylcarbonyl.
  • Each R independently represents hydrogen, formyl, d-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy,
  • Each R 2 and R 3 independently of each other represents hydrogen, formyl, Ci-C 4 alkyl, d- C 4 haloalkyl, C 2 -C 4 alkylcarbonyl, C 2 -C 4 alkoxycarbonyl, benzyl or phenyl; or
  • R 2 and R 3 together with the nitrogen atom to which they are attached form a three to six- membered saturated cyclic group which optionally contains either one oxygen atom or one sulphur atom.
  • each R 2 and R 3 independently of each other represents hydrogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, benzyl or phenyl; or
  • R 2 and R 3 together with the nitrogen atom to which they are attached form a three to six- membered saturated cyclic group which optionally contains either one oxygen atom or one sulphur atom.
  • R 4 represents phenyl optionally substituted by fluoro, CN, OH, methyl, ethyl, n-propyl, iso- propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 -CH 3 , CF 2 - CF 3 , OMe, OEt, OiPr, OPr, OCHF 2 and OCF 3 .
  • Each R 5 independently represents hydrogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, C 3 -C 5 alkenyl, C 3 -
  • Each R 7 and R 8 independently of each other represents hydrogen, Ci-C 4 alkyl, d- C 4 fluoroalkyl, benzyl or phenyl; or
  • R 7 and R 8 together with the nitrogen atom to which they are attached form aziridine, azetidine, pyrolidine, piperidine, morpholine, and thiomorpholine.
  • each R 7 and R 8 independently of each other represents hydrogen, methyl, ethyl, propyl, isopropyl, CHF 2 , CF 3 , benzyl or phenyl.
  • each R 7 and R 8 independently of each other represents hydrogen, methyl, ethyl, propyl or isopropyl.
  • D represents Ci-C 4 alkyl, C 2 -C 5 alkenyl, C 2 -C 5 alkynyl, C 3 -C 6 cycloalkyl, benzyl, phenyl each of which are optionally substituted by one or more groups independently selected from halogen, cyano, hydroxy, mercapto, Ci-C 4 haloalkyl, Ci-C 4 alkoxy, formyl, C 2 -C 5 alkylcarbonyl, Ci-C 4 alkoxycarbonyl, d- C 4 alkylthio, Ci-C 4 haloalkylthio, C 1 -C 4 alkylsulfinyl and Ci-C 4 alkylsulfonyl.
  • Z represents methlyene or ethylene, wherein the methlyene and ethylene are optionally substituted by one or more groups independently selected from fluorine, CN, OH, methyl, ethyl, propyl, iso-propyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 -CF 3 , CN, OMe, OEt, COMe, COEt, COiPr, COtBu, C0 2 Me, C0 2 Et, C0 2 iPr, and C0 2 tBu;
  • R 9 represents hydrogen, d-C 6 alkyl, d-C 6 alkenyl or CrC 6 alkynyl wherein the alkyl, alkenyl and alkynyl are optionally be optionally substituted by one or more groups independently selected from halogen, CN, OH, Ci-C 4 alkyl, C 2 -C 4 alkenyl, Ci-C 4 fluoroalkyl, Ci-C 4 alkoxy, and C 2 -C 5 alkylcarbonyl; or R 9 represents a five- or six-membered saturated or partially saturated monocyclic system which contains one or two members selected from the group consisting of N, N(R 11 ), O and S, optionally substituted by one or more groups independently selected from the group consisting of halogen, CN, N0 2 , OH, SH, CHO, d-C 4 alkyl, d-C 4 haloalkyl, C 3 -C 6 cycloalkyl, C 2 -C 5 alkeny
  • R 9 represents a C 3 -C 8 carbocyclic system, which may be partially saturated or fully saturated and is optionally substituted by one or more groups independently selected from halogen, CN, N0 2 , OH, SH, CHO, COOH, d-d alkyl, d-d alkoxy, d-d haloalkyl, d-d haloalkoxy, C 3 -C 6 cycloalkyl and Ci-C 4 alkylcarbonyl; or
  • R 9 represents NHR 4 ;
  • each R independently represents hydrogen, formyl, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy,
  • each R 2 and R 3 independently of each other represents hydrogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, benzyl or phenyl; or
  • R 2 and R 3 together with the nitrogen atom to which they are attached form a three to six- membered saturated cyclic group which optionally contains either one oxygen atom or one sulphur atom;
  • R 7 and R 8 together with the nitrogen atom to which they are attached form aziridine, azetidine, pyrolidine, piperidine, morpholine, and thiomorpholine.
  • m represents 0 or 1 ;
  • R 9 represents hydrogen, d-C 6 alkyl, d-C 6 alkenyl or d-C 6 alkynyl, wherein the alkyl, alkenyl and alkynyl are optionally substituted by one or more groups selected from chloro, fluoro, bromo, CN, OH, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 -CH 3 , CF 2 -CF 3 , OMe, OEt, OiPr, OPr, OCHF 2 , and OCF 3 ;
  • R 9 represents a five- or six-membered saturated monocyclic system which contains one or two members selected from the group consisting of N, N(R 11 ), O and S, optionally substituted by one or more groups independently selected from chloro, fluoro, bromo, CN, N0 2 , OH, SH, CHO, Ci-C 4 alkyl, Ci-C 4 fluoroalkyl, d-C 4 alkoxy, Ci-C 4 fluoroalkoxy, Ci-C 4 alkylcarbonyl and Ci-C 4 alkoxycarbonyl; or
  • R 9 represents a five- or six-membered aromatic monocyclic system which contains one or two members selected from the group consisting of N, N(R 16 ), O and S, optionally substituted by one or more groups independently selected from chloro, fluoro, bromo, CN, N0 2 , OH, SH, CHO, Ci-C 4 alkyl, Ci-C 4 fluoroalkyl, Ci-C 4 alkoxy, Ci-C 4 fluoroalkoxy, Ci-C 4 alkylcarbonyl, and Ci-C 4 alkoxycarbonyl; or
  • R 9 represents a five or six membered carbocyclic system which can be partially saturated or fully saturated and is optionally substituted by one or more groups independently selected from chloro, fluoro, bromo, CN, N0 2 , OH, SH, Ci-C 4 alkyl, Ci-C 4 alkoxy, Ci-C 4 fluoroalkyl and Ci-C 4 fluoroalkoxy; or
  • R 9 represents NHR 4 ;
  • R 0 represents hydrogen or methyl
  • each R 7 and R 8 independently of each other represents hydrogen, methyl, ethyl, propyl, isopropyl, CHF 2 , CF 3 , benzyl or phenyl.
  • m represents 0 or 1 ;
  • Z represents methylene or ethylene, each of which is optionally substituted by one or more methyl groups
  • R 9 represents hydrogen, d-C 6 alkyl, d-C 6 alkenyl or d-C 6 alkynyl, wherein the alkyl, alkenyl and alkynyl are optionally substituted by one or more groups selected from fluoro, CN , OH, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 - CH 3 , CF 2 -CF 3 OMe, OEt, OiPr, OPr; or
  • R 9 represents a five- or six-membered saturated monocyclic system which contains one or two members selected from the group consisting of N, N(R 11 ), O and S, optionally substituted by one or more groups independently selected from chloro, fluoro, bromo, CN, N0 2 , OH , SH , methyl, ethyl, n- propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 - CH 3 , CF 2 -CF 3 , OMe, OEt, OiPr, OnPr, OCHF 2 and OCF 3 ; or
  • R 9 represents a five- or six-membered aromatic monocyclic system which contains one or two members selected from the group consisting of N, N(R 16 ), O and S, optionally substituted by one or more groups independently selected from fluoro, CN, N0 2 , OH, SH, CHO, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 -CH 3 , CF 2 -CF 3 , OMe, OEt, OiPr, OPr, OCHF 2 , OCF 3 , SCHF 2 , SCF 3 , COMe, COEt, COiPr, COtBu, C0 2 Me, C0 2 Et, C0 2 iPr, and C0 2 tBu
  • R 9 represents a five or six membered carbocyclic system which can be partially saturated or fully saturated and is optionally substituted by one or more groups independently selected from fluoro, CN, N0 2 , OH, SH, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 -CH 3 , CF 2 -CF 3 , OMe, OEt, OiPr, OPr, OCHF 2 and OCF 3 ; or
  • R 9 represents NHR 4 ;
  • each R 7 and R 8 independently of each other, represents hydrogen, methyl, ethyl, propyl or isopropyl.
  • R 9 represents hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, wherein the alkyl, alkenyl, alkynyl and cycloalkoxyare optionally substituted by one or more groups independently selected from halogen, hydroxyl, cyano, N0 2 , OH, SH, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynl, d-C 6 haloalkyl, d-C 6 alkoxy, C 3 -C 8 cycloalkyl C 3 -C 8 cycloalkoxy, formyl, C 2 - C 6 alkylcarbonyl, d-C 6 alkylthio, d-C 6 alkylsulfinyl and d-C 6 alkylsulfonyl.
  • R 9 represents hydrogen, d-C 6 alkyl, d-C 6 alkenyl or d- C 6 alkynyl wherein the alkyl, alkenyl and alkynyl are optionally be optionally substituted by one or more groups independently selected from halogen, CN, OH, d-C 4 alkyl, C 2 -C 4 alkenyl, d-C 4 fluoroalkyl, d- dalkoxy, and C 2 -C 5 alkylcarbonyl.
  • R 9 represents hydrogen, d-C 6 alkyl, d-C 6 alkenyl or d-C 6 alkynyl, wherein the alkyl, alkenyl and alkynyl are optionally substituted by one or more groups selected from chloro, fluoro, bromo, CN, OH, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso- butyl, sec-butyl, tert-butyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 -CH 3 , CF 2 -CF 3 , OMe, OEt, OiPr, OPr, OCHF 2 , and OCF 3 .
  • R 9 represents hydrogen, d-C 6 alkyl, d-C 6 alkenyl or d-C 6 alkynyl, wherein the alkyl, alkenyl and alkynyl are optionally substituted by one or more groups selected from fluoro, CN, OH, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 -CH 3 , CF 2 -CF 3, OMe, OEt, OiPr, OPr.
  • R 9 represents hydrogen, d-C 6 alkyl, d-C 6 alkenyl or Ci-C 6 alkynyl, wherein the alkyl, alkenyl and alkynyl are optionally substituted by one or more groups selected from fluoro, CN, OH, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 -CH 3 , CF 2 -CF 3
  • R represents D-A-Ci-C 6 alkyl-, D-A-Ci-C 6 alkyl-, D-A-d-C 6 alkyl-, D-A-Ci-C 6 alkyl-, D-A-Ci-C 6
  • R 9 represents a five- or six-membered saturated monocyclic system which contains one or two members selected from the group consisting of N , N(R ), O and S, optionally substituted by one or more groups independently selected from chloro, fluoro, bromo, CN, N0 2 , OH, SH, CHO, d-C 4 alkyl, d-C 4 fluoroalkyl, d-C 4 alkoxy, d-C 4 fluoroalkoxy, d-C 4 alkylcarbonyl and Ci-C 4 alkoxycarbonyl.
  • R 9 represents a five- or six-membered saturated monocyclic system which contains one or two members selected from the group consisting of N , N(R ), O and S, optionally substituted by one or more groups independently selected from chloro, fluoro, bromo, CN, N0 2 , OH , SH , methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert- butyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 -CH 3 , CF 2 -CF 3 , OMe, OEt, OiPr, OnPr, OCHF 2 and OCF 3 .
  • R represents a five- or six-membered aromatic monocyclic system which contains one or two members selected from the group consisting of N, N(R 16 ), O and S, optionally substituted by one or more groups independently selected from chloro, fluoro, bromo, CN, N0 2 , OH, SH, CHO, d-C 4 alkyl, Ci-C 4 fluoroalkyl, d-C 4 alkoxy, d-C 4 fluoroalkoxy, Ci-C 4 alkylcarbonyl, and Ci-C 4 alkoxycarbonyl.
  • R 9 represents a five- or six-membered aromatic monocyclic system which contains one or two members selected from the group consisting of N, N(R 16 ), O and S, optionally substituted by one or more groups independently selected from fluoro, CN, N0 2 , OH, SH, CHO, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 -CH 3 , CF 2 -CF 3 , OMe, OEt, OiPr, OPr, OCHF 2 , OCF 3 , SCHF 2 , SCF 3 , COMe, COEt, COiPr, COtBu, C0 2 Me, C0 2 Et, C0 2 iP
  • groups independently selected from chloro, fluoro, bromo, CN, N0 2 , OH, SH, CHO, COOH, d- C 4 alkyl, Ci-C 4 alkoxy, Ci-C 4 fluoroalkyl, C 3 -C 6 cycloalkyl, C 2 -C 4 alkenyl, Ci-C 4 flu
  • R 9 represents a C 3 -C 8 carbocyclic system, which may be partially saturated or fully saturated and is optionally substituted by one or more groups independently selected from halogen, CN, N0 2 , OH, SH, CHO, COOH, d-C 4 alkyl, d-C 4 alkoxy, d- C 4 haloalkyl, Ci-C 4 haloalkoxy, C 3 -C 6 cycloalkyl and Ci-C 4 alkylcarbonyl.
  • R 9 represents a five or six membered carbocyclic system which can be partially saturated or fully saturated and is optionally substituted by one or more groups independently selected from chloro, fluoro, bromo, CN, N0 2 , OH, SH, Ci-C 4 alkyl, Ci-C 4 alkoxy, d- dfluoroalkyl and Ci-C 4 fluoroalkoxy.
  • R 9 represents a five or six membered carbocyclic system which can be partially saturated or fully saturated and is optionally substituted by one or more groups independently selected from fluoro, CN, N0 2 , OH, SH, methyl, ethyl, n-propyl, iso-propyl, n- butyl, iso-butyl, sec-butyl, tert-butyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 -CH 3 , CF 2 -CF 3 , OMe, OEt, OiPr, OPr, OCHF 2 and OCF 3.
  • groups independently selected from fluoro, CN, N0 2 , OH, SH, methyl, ethyl, n-propyl, iso-propyl, n- butyl, iso-butyl, sec-butyl, tert-butyl, CH
  • R 9 represents NHR 4 , wherein R 4 is as described above.
  • Z represents methylene or ethylene each of which is optionally substituted by one or more substituents independently selected from methyl, ethyl, OH, CN, CF 3 , OMe, OEt, C0 2 Me, C0 2 Et and C0 2 iPr;
  • n 0 or 1
  • R 9 represents H, NHR 4 , Ci-C 6 alkyl, Ci-C 6 alkenyl, Ci-C 6 alkoxy, Ci-C 6 alkenoxy, C 3 -
  • C 6 cycloalkylmethoxy, phenyl, benzyl or a five- or six-membered saturated or aromatic monocyclic system which contains one or two members selected from the group consisting of N and O, each of which are optionally substituted by one or more groups independently selected from chloro, fluoro, bromo, CN, OH, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 -CH 3 , CF 2 -CF 3 , OMe, OEt, OiPr, OPr, OCHF 2 , OCF 3 ;
  • R 4 represents phenyl optionally substituted by fluoro, CN, OH, methyl, ethyl, n-propyl, iso- propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 -CH 3 , CF 2 - CF 3 , OMe, OEt, OiPr, OPr, OCHF 2 and OCF 3 .
  • Z represents methylene or ethylene each of which is optionally substituted by one or more substituents independently selected from methyl, ethyl, OH, CN, CF 3 , OMe, OEt, C0 2 Me, C0 2 Et and C0 2 iPr;
  • n 0 or 1
  • R 9 represents NHR 14 , d-C 6 alkyl, Ci-C 6 alkenyl, d-C 6 alkoxy, d-C 6 alkenoxy, C 3 - C 6 cycloalkylmethoxy, phenyl, benzyl or a five- or six-membered saturated or aromatic monocyclic system which contains one or two members selected from the group consisting of N and O, each of which are optionally substituted by one or more groups independently selected from chloro, fluoro, bromo, CN, OH, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 -CH 3 , CF 2 -CF 3 , OMe, OEt, OiPr, OPr,
  • R 4 represents phenyl optionally substituted by fluoro, CN, OH, methyl, ethyl, n-propyl, iso- propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 -CH 3 , CF 2 -CH 3 , CF 2 - CF 3 , OMe, OEt, OiPr, OPr, OCHF 2 and OCF 3 .
  • Z represents methylene or ethylene each of which is optionally substituted by one or more substituents independently selected from methyl, ethyl, OH, CN, CF 3 , OMe, OEt, C0 2 Me, C0 2 Et and C0 2 iPr;
  • n 0 or 1
  • R 9 represents d-C 6 alkyl, d-C 6 alkenyl, d-C 6 alkoxy, d-C 6 alkenoxy, C 3 -C 6 cycloalkylmethoxy, phenyl, benzyl or a five- or six-membered saturated or aromatic monocyclic system which contains one or two members selected from the group consisting of N and O, each of which are optionally substituted by one or more groups independently selected from chloro, fluoro, bromo, CN, OH, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CH 2 F, CHF 2 , CF 3 , CHF-CH 3 , CF 2 - CH 3 , CF 2 -CH 3 , CF 2 -CF 3 , OMe, OEt, OiPr, OPr, OCHF 2 and
  • R and R 2 independently of each other represent hydrogen, d-C 4 alkyl or cyclopropyl;
  • R 4 represents hydrogen;
  • R 6 , R 7 and R 9 independently of each other represent hydrogen, halogen, CN, d-C 4 alkyl, d- C 4 alkoxy, Ci-C 4 haloalkyl or C1-C4 haloalkoxy.
  • R and R 2 independently of each other represent hydrogen, methyl, ethyl, isopropyl, n-propyl or cyclopropyl;
  • R 3 represents hydrogen, chloro, methyl or ethyl
  • R 4 represents hydrogen
  • R 6 , R 7 and R 8 independently of each other represent hydrogen, fluoro, chloro, bromo, CN, methyl, ethyl, propyl, OMe, OEt, CHF 2 , CF 3 or OCHF 2 .
  • R represents methyl
  • R 2 represents ethyl
  • R 3 represents methyl
  • R 4 , R 6 , R 7 and R 8 represent hydrogen.
  • the present invention further provides novel intermediate compounds of the formula (XIX).
  • R 3 , R 4 , R 6 , R 7 and R 8 are as defined herein for a compound of formula (I) and R is defined as hydrogen or C0 2 tBu;
  • X is CI, Br, I, boronic ester, boronic acid, tri-alkylstannane, CN, CH 2 OH, CH(Me)OH, CHO, C(0)Me, C0 2 Me, and C0 2 Et.
  • X is CI, Br, I, CN, CH 2 OH, CH(Me)OH, CHO, C(0)Me, C0 2 Me, C0 2 Et, B(OH) 2 , B(OMe) 2 , B[0 2 C 2 (Me) 4 ], SnMe 3 , or SnBu 3 .
  • X is CI, Br, I, B(OH) 2 , B(OMe) 2 ,
  • X is CI, Br or I.
  • X is bromine
  • R is hydrogen
  • the invention is further illustrated by making available the following individual compounds of formula (I) listed below in Tables 1 to 16.
  • Tables 1 to 16 which follow Table A below, make available 552 compounds of the formula (I) in which R , R 2 and R 5 are the substituents defined in Table A and the remaining substituents are defined in each of Tables 1 to 16 respectively.
  • Table 1 individualises 552 compounds of formula (I) wherein R , R 2 and R 5 are as defined in each respective row of Table A, and the remaining substituents are as defined in Table 1.
  • Table 2 individualises 552 compounds of formula (I) wherein R , R 2 and R 5 are as defined in each respective row of Table A, and the remaining substituents are as defined in Table 2; and so on for Tables 3 to 16.
  • Table A discloses 552 sets of meanings of the variables R , R 2 and R 5 in a compound of formula (IA), as follows:
  • A.221 H isopropyl 3-(difluoromethoxy)propyl
  • A.229 H isopropyl (4-difluoromethyl)cyclohexylmethyl
  • A.269 H isopropyl tert-bu tyl 4-m ethylpi perid i ne- 1 -carboxylate
  • A.405 H isopropyl [4-(difluoromethyl)phenyl]ethyl
  • A.429 H isopropyl [4-(difluoromethyl)phenyl]methyl
  • A.501 H isopropyl [3-(difluoromethyl)phenoxy]methyl
  • Table 1 discloses 552 compounds of formula (I) wherein each of R 3 , R 4 , R 6 , R 7 and R ! are hydrogen and each of the variables R , R 2 and R 5 has the specific meaning given in the corresponding row of Table A.
  • compound 1.1 has the following structure:
  • Table 2 discloses 552 compounds of formula (I) wherein R 3 is methyl, each of R 4 , R 6 , R 7 and R 8 are hydrogen and each of the variables R , R 2 and R 5 has the specific meaning given in the corresponding row of Table A.
  • Table 3 discloses 552 compounds of formula (I) wherein R 3 is ethyl, each of R 4 , R 6 , R 7 and R 8 are hydrogen and each of the variables R , R 2 and R 5 has the specific meaning given in the corresponding row of Table A.
  • Table 4 discloses 552 compounds of formula (I) wherein R 3 is cycloproply, each of R 4 , R 6 , R 7 and R 8 are hydrogen and each of the variables R , R 2 and R 5 has the specific meaning given in the corresponding row of Table A.
  • Table 5 discloses 552 compounds of formula (I) wherein R 3 is methyl, R 8 is chloro, each of R 4 , R 6 and R 7 are hydrogen and each of the variables R , R 2 and R 5 has the specific meaning given in the corresponding row of Table A.
  • Table 6 discloses 552 compounds of formula (I) wherein R 3 is methyl, R 8 is methyl, each of R 4 , R 6 and R 7 are hydrogen and each of the variables R , R 2 and R 5 has the specific meaning given in the corresponding row of Table A.
  • Table 7 discloses 552 compounds of formula (I) wherein R 3 is methyl, R 8 is methoxy, each of R 4 , R 6 and R 7 are hydrogen and each of the variables R , R 2 and R 5 has the specific meaning given in the corresponding row of Table A.
  • Table 8 discloses 552 compounds of formula (I) wherein R 3 is methyl, R 8 is cyano, each of R 4 , R 6 and R 7 are hydrogen and each of the variables R , R 2 and R 5 has the specific meaning given in the corresponding row of Table A.
  • Table 9 discloses 552 compounds of formula (I) wherein R 3 is methyl, R 7 is chloro, each of R 4 , R 6 and R 8 are hydrogen and each of the variables R , R 2 and R 5 has the specific meaning given in the corresponding row of Table A.
  • Table 10 discloses 552 compounds of formula (I) wherein R 3 is methyl, R 7 is methyl, each of R 4 , R 6 and R 8 are hydrogen and each of the variables R , R 2 and R 5 has the specific meaning given in the corresponding row of Table A.
  • Table 1 1 discloses 552 compounds of formula (I) wherein R 3 is methyl, R 8 is methoxy, each of R 4 , R 6 and R 7 are hydrogen and each of the variables R , R 2 and R 5 has the specific meaning given in the corresponding row of Table A.
  • Table 12 discloses 552 compounds of formula (I) wherein R 3 is methyl, R 8 is cyano, each of R 4 , R 6 and R 7 are hydrogen and each of the variables R , R 2 and R 5 has the specific meaning given in the corresponding row of Table A.
  • Table 13 discloses 552 compounds of formula (I) wherein R 3 is methyl, R 6 is chloro, each of R 4 , R 7 and R 8 are hydrogen and each of the variables R , R 2 and R 5 has the specific meaning given in the corresponding row of Table A.
  • Table 14 discloses 552 compounds of formula (I) wherein R 3 is methyl, R 6 is methyl, each of R 4 , R 7 and R 8 are hydrogen and each of the variables R , R 2 and R 5 has the specific meaning given in the corresponding row of Table A.
  • Table 15 discloses 552 compounds of formula (I) wherein R 3 is methyl, R 6 is methoxy, each of R 4 , R 7 and R 8 are hydrogen and each of the variables R , R 2 and R 5 has the specific meaning given in the corresponding row of Table A.
  • Table 16 discloses 552 compounds of formula (I) wherein R 3 is methyl, R 6 is cyano, each of R 4 , R 7 and R 8 are hydrogen and each of the variables R , R 2 and R 5 has the specific meaning given in the corresponding row of Table A.
  • 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, in particular against diseases that are caused by fungi.
  • Compounds of formula I and fungicidal compositions containing them may be used to control plant diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete,
  • 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.
  • plants refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
  • locus means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
  • the compounds of formula I can be used in the agricultural sector and related fields of use e.g. as active ingredients for controlling plant pests or on non-living materials for control of spoilage microorganisms or organisms potentially harmful to man.
  • 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 of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later from phytopathogenic micro-organisms.
  • fungicide as used herein means a compound that controls, modifies, or prevents the growth of fungi.
  • fungicidally effective amount means the quantity of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Controlling or modifying effects include all deviation from natural development, such as killing, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection.
  • a preferred method of applying a compound of formula (I) 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.
  • compounds of formula (I) as dressing agents for the treatment of plant propagation material, in particular of seeds and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
  • the propagation material can be treated with a composition comprising a compound of formula I before planting: seed, for example, can be dressed before being sown.
  • the active ingredients according to the invention can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation.
  • the composition can also be applied to the planting site when the propagation material is being planted, for example, to the seed furrow during sowing.
  • the invention relates also to such methods of treating plant propagation material and to the plant propagation material so treated.
  • plant propagation material denotes all generative parts of a plant, for example seeds or vegetative parts of plants such as cuttings and tubers. It includes seeds in the strict sense, as well as roots, fruits, tubers, bulbs, rhizomes, and parts of plants.
  • 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 invention could be used to protect non-living materials from fungal attack, e.g. lumber, wall boards and paint.
  • the compounds of formula I are for example, effective against Fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses.
  • pathogens may include:
  • Oomycetes including Phytophthora diseases such as those caused by Phytophthora capsici, Phytophthora infestans, Phytophthora sojae, Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora and Phytophthora erythroseptica; Pythium diseases such as those caused by Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare and Pythium ultimum; diseases caused by Peronosporales such as Peronospora destructor, Peronospora parasitica, Plasmopara viticola, Plasmopara halstedii, Pseudoperonospora cubensis, Albugo Candida, Sclerophthora macrospora and Br
  • Ascomycetes including blotch, spot, blast or blight diseases and/or rots for example those caused by Pleosporales such as Stemphylium solani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phoma destructiva,
  • Pleosporales such as Stemphylium solani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phoma destructiva,
  • Ophiobolus graminis Leptosphaeria maculans, Hendersonia creberrima, Helminthosporium triticirepentis, Setosphaeria turcica, Drechslera glycines, Didymella bryoniae, Cycloconium
  • Mycosphaerella fijiensis Mycosphaerella graminicola, Mycovellosiella koepkeii, Phaeoisariopsis bataticola, Pseudocercospora vitis, Pseudocercosporella herpotrichoides, Ramularia beticola, Ramularia collo-cygni, Magnaporthales such as Gaeumannomyces graminis, Magnaporthe grisea, Pyricularia oryzae, Diaporthales such as Anisogramma anomala, Apiognomonia errabunda, Cytospora platani, Diaporthe phaseolorum, Discula destructiva, Gnomonia fructicola, Greeneria uvicola, Melanconium juglandinum, Phomopsis viticola, Sirococcus clavigignenti-juglandacearum, Tubakia dryina, Dicarpella spp.
  • Valsa ceratosperma and others such as Actinothyrium graminis, Ascochyta pisi, Aspergillus flavus, Aspergillus fumigatus, Aspergillus nidulans, Asperisporium caricae, Blumeriella jaapii, Candida spp.
  • Phialophora gregata Phyllachora pomigena, Phymatotrichum omnivora, Physalospora abdita, Plectosporium tabacinum, Polyscytalum pustulans, Pseudopeziza medicaginis, Pyrenopeziza brassicae, Ramulispora sorghi, Rhabdocline pseudotsugae, Rhynchosporium secalis, Sacrocladium oryzae, Scedosporium spp., Schizothyrium pomi, Sclerotinia sclerotiorum, Sclerotinia minor,
  • Sclerotium spp. Typhula ishikariensis, Seimatosporium mariae, Lepteutypa cupressi, Septocyta ruborum, Sphaceloma perseae, Sporonema phacidioides, Stigmina palmivora, Tapesia yallundae, Taphrina bullata, Thielviopsis basicola, Trichoseptoria fructigena, Zygophiala jamaicensis; powdery mildew diseases for example those caused by Erysiphales such as Blumeria graminis, Erysiphe polygoni, Uncinula necator, Sphaerotheca fuligena, Podosphaera leucotricha, Podospaera macularis Golovinomyces cichoracearum, Leveillula taurica, Microsphaera diffusa, Oidiopsis gossypii,
  • Phyllactinia guttata and Oidium arachidis molds for example those caused by Botryosphaeriales such as Dothiorella aromatica, Diplodia seriata, Guignardia bidwellii, Botrytis cinerea, Botryotinia allii, Botryotinia fabae, Fusicoccum amygdali, Lasiodiplodia theobromae, Macrophoma theicola,
  • Macrophomina phaseolina Phyllosticta cucurbitacearum
  • anthracnoses for example those caused by Glommerelales such as Colletotrichum gloeosporioides, Colletotrichum lagenarium, Colletotrichum gossypii, Glomerella cingulata, and Colletotrichum graminicola
  • wilts or blights for example those caused by Hypocreales such as Acremonium strictum, Claviceps purpurea, Fusarium culmorum, Fusarium graminearum, Fusarium virguliforme, Fusarium oxysporum, Fusarium subglutinans, Fusarium oxysporum f.sp. cubense, Gerlachia nivale, Gibberella fujikuroi, Gibberella zeae,
  • Gliocladium spp. Myrothecium verrucaria, Nectria ramulariae, Trichoderma viride, Trichothecium roseum, and Verticillium theobromae.
  • Basidiomycetes including smuts for example those caused by Ustilaginales such as
  • Ustilaginoidea virens Ustilago nuda, Ustilago tritici, Ustilago zeae, rusts for example those caused by Pucciniales such as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata, Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp. Hordei, Puccinia striiformis f.sp. Secalis,
  • Pucciniastrum coryli or Uredinales such as Cronartium ribicola, Gymnosporangium juniper!- viginianae, Melampsora medusae, Phakopsora pachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzschelia discolor and Uromyces viciae-fabae; and other rots and diseases such as those caused by Cryptococcus spp., Exobasidium vexans, Marasmiellus inoderma, Mycena spp., Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisum, Laetisaria fuciformis, Waitea circinata, Rhizoctonia solani, Thanetephorus cucurmeris, Entyloma dahliae,
  • Blastocladiomycetes such as Physoderma maydis.
  • Mucoromycetes such as Choanephora cucurbitarum.; Mucor spp.; Rhizopus arrhizus, As well as diseases caused by other species and genera closely related to those listed above.
  • the compounds and compositions comprising them may also have activity against bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Strptomyces scabies and other related species as well as certain protozoa.
  • Crops of useful plants in which the composition according to the invention can be used include perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St.
  • perennial and annual crops such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries
  • cereals for example barley, maize (corn), mille
  • Augustine grass and Zoysia grass herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.
  • herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme
  • legumes for example beans, lentils, peas and soya beans
  • Crops are to be understood as being those which are naturally occurring, obtained by conventional methods of breeding, or obtained by genetic engineering. They include crops which contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).
  • output traits e.g. improved storage stability, higher nutritional value and improved flavour.
  • Crops are to be understood as also including those crops which have been rendered tolerant to herbicides like bromoxynil or classes of herbicides such as ALS-, EPSPS-, GS-, HPPD- and PPO- inhibitors.
  • herbicides like bromoxynil or classes of herbicides such as ALS-, EPSPS-, GS-, HPPD- and PPO- inhibitors.
  • An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer canola.
  • crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®.
  • Crops are also to be understood as being those which naturally are or have been rendered resistant to harmful insects. This includes plants transformed by the use of recombinant DNA techniques, for example, to be capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria. Examples of toxins which can be expressed include ⁇ -endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of bacteria colonising nematodes, and toxins produced by scorpions, arachnids, wasps and fungi.
  • Vip vegetative insecticidal proteins
  • insecticidal proteins of bacteria colonising nematodes and toxins produced by scorpions, arachnids, wasps and fungi.
  • An example of a crop that has been modified to express the Bacillus thuringiensis toxin is the Bt maize KnockOut® (Syngenta Seeds).
  • An example of a crop comprising more than one gene that codes for insecticidal resistance and thus expresses more than one toxin is VipCot® (Syngenta Seeds).
  • Crops or seed material thereof can also be resistant to multiple types of pests (so-called stacked transgenic events when created by genetic modification).
  • a plant can have the ability to express an insecticidal protein while at the same time being herbicide tolerant, for example Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).
  • the compounds of formula (I) can be used in unmodified form or, preferably, together with carriers and adjuvants conventionally employed in the art of formulation.
  • 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) as active ingredient and an inert carrier, is applied to the plants, to parts thereof or the locus thereof.
  • 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.
  • 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.
  • 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
  • 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 10g to 1 kg a.i./ha, most preferably from 20g to 600g a.i./ha.
  • convenient rates of application are from 10mg to 1g 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.
  • agronomic chemicals include insecticides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection, as well as plant nutrients and plant fertilizers.
  • the present invention provides a composition
  • a composition comprising a compound of formula (I) according to the present invention together with one or more pesticides, plant nutrients or plant fertilizers.
  • the combination may also encompass specific plant traits incorporated into the plant using any means, for example conventional breeding or genetic modification.
  • Such compositions may also contain one or more inert carriers as described above.
  • the invention also provides for the use of provides a composition comprising a compound of formula (I) according to the present invention together with one or more pesticides, plant nutrients, plant fertilizers, synergists, herbicides or plant growth regulators, where appropriate.
  • the combination may also encompass specific plant traits incorporated into the plant using any means, for example conventional breeding or genetic modification.
  • Suitable examples of plant nutrients or plant fertilizers are calcium sulfate (CaS0 4 ), calcium nitrate (Ca(N0 3 )2.4H 2 0), calcium carbonate (CaC0 3 ), potassium nitrate (KN0 3 ), magnesium sulfate (MgS0 4 ), potassium hydrogen phosphate (KH 2 P0 4 ), manganese sulfate (MnS0 4 ), copper sulfate (CuS0 4 ), zinc sulfate (ZnS0 4 ), nickel chloride (NiCI 2 ), cobalt sulfate (CoS0 4 ), potassium hydroxide (KOH), sodium chloride (NaCI), boric acid (H 3 B0 3 ) and metal salts thereof (Na 2 Mo0 4 ).
  • CaS0 4 calcium sulfate
  • Ca(N0 3 )2.4H 2 0 calcium carbonate
  • CaC0 3 calcium carbonate
  • KN0 3 potassium nitrate
  • the nutrients may be present in an amount of 5% to 50% by weight, preferably of 10% to 25% by weight or of 15% to 20% by weight each.
  • Preferred additional nutrients are urea ((NH 2 ) 2 CO), melamine (C 3 H 6 N 6 ), potassium oxide (K 2 0), and inorganic nitrates.
  • the most preferred additional plant nutrient is potassium oxide. Where the preferred additional nutrient is urea, it is present in an amount of generally 1 % to 20% by weight, preferably 2% to 10% by weight or of 3% to 7% by weight.
  • Suitable additional active ingredients include the following acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenical fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged diphenyl fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, , dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine
  • triazolopyrimidine fungicides triazolopyrimidine fungicides, urea fungicides, valinamide fungicides, and zinc fungicides.
  • suitable additional active ingredients also include the following: 3-difluoromethyl-1- methyl-1 H-pyrazole-4-carboxylic acid (9-dichloromethylene-1 ,2,3,4-tetrahydro-1 ,4-methano- naphthalen-5-yl)-amide , 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid methoxy-[1-methyl- 2-(2,4,6-trichlorophenyl)-ethyl]-amide , 1-methyl-3-difluoromethyl-1 H-pyrazole-4-carboxylic acid (2- dichloromethylene-3-ethyl-1-methyl-indan-4-yl)-amide (1072957-71-1 ), 1-methyl-3-difluoromethyl-1 H- pyrazole-4-carboxylic acid (4'-methylsulfanyl-biphenyl-2-yl)-amide, 1-methyl-3-difluoromethyl-4H- pyrazo
  • phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl- 4-chlorophenol, phenoxyethanol, dichlorophene, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2- benzyl-4-chlorophenol, 5-hydroxy-2(5H)-furanone; 4,5-dichlorodithiazolinone, 4,5-benzodithiazolinone, 4,5-trimethylenedithiazolinone, 4,5-dichloro-(3H)-1 ,2-dithiol-3-one, 3,5-dimethyl-tetrahydro-1 ,3,5- thiadiazine-2-thione, N-(2-p-chlorobenzoylethyl)-hexaminium chloride, acibenzolar, acypetacs, alanycarb, albendazole, aldimorph, allicin, allyl
  • imibenconazole iminoctadine, iminoctadine triacetate, inezin, iodocarb, ipconazole, iprobenfos, iprodione, iprovalicarb, isopropanyl butyl carbamate, isoprothiolane, isopyrazam, isotianil, isovaledione, izopamfos, kasugamycin, kresoxim-methyl, LY186054, LY21 1795, LY248908, mancozeb, mandipropamid, maneb, mebenil, mecarbinzid, mefenoxam, mepanipyrim, mepronil, mercuric chloride, mercurous chloride, meptyldinocap, metalaxyl, metalaxyl-M, metam, metazoxolon, metconazole, methasulfocarb, methfuroxam, methyl
  • the compounds of the invention may also be used in combination with anthelmintic agents.
  • anthelmintic agents include, compounds selected from the macrocyclic lactone class of compounds such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin derivatives as described in EP- 357460, EP- 444964 and EP-594291.
  • Additional anthelmintic agents include semisynthetic and biosynthetic avermectin/milbemycin derivatives such as those described in US-5015630, WO-9415944 and WO- 9522552. Additional anthelmintic agents include the benzimidazoles such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, and other members of the class. Additional anthelmintic agents include imidazothiazoles and tetrahydropyrimidines such as tetramisole, levamisole, pyrantel pamoate, oxantel or morantel.
  • Additional anthelmintic agents include flukicides, such as triclabendazole and clorsulon and the cestocides, such as praziquantel and epsiprantel.
  • the compounds of the invention may be used in combination with derivatives and analogues of the paraherquamide/marcfortine class of anthelmintic agents, as well as the antiparasitic oxazolines such as those disclosed in US-5478855, US- 4639771 and DE-19520936.
  • the compounds of the invention may be used in combination with derivatives and analogues of the general class of dioxomorpholine antiparasitic agents as described in WO-9615121 and also with anthelmintic active cyclic depsipeptides such as those described in WO-961 1945, WO-9319053, WO- 9325543, EP-626375, EP-382173, WO-9419334, EP-382173, and EP-503538.
  • the compounds of the invention may be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron;
  • ectoparasiticides for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron;
  • ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.
  • the compounds of the invention may be used in combination with terpene alkaloids, for example those described in International Patent Application Publication Numbers W095/19363 or WO04/72086, particularly the compounds disclosed therein.
  • Organophosphates acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, bromophos, bromophos-ethyl, cadusafos, chlorethoxyphos, chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demeton-S-methyl, demeton-S-methyl sulphone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosthiazate, heptenophos, isazophos, isothioate, isoxathion, malathion, me
  • Carbamates alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801 , isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenylbutyryl(methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, UC-51717.
  • Arthropod growth regulators a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox, etoxazole, chlorfentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide; c) juvenoids: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen.
  • antiparasitics acequinocyl, amitraz, AKD-1022, ANS-1 18, azadirachtin, Bacillus thuringiensis, bensultap, bifenazate, binapacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorobenzilate, chlordimeform, chlorfenapyr, chromafenozide, clothianidine, cyromazine, diacloden, diafenthiuron, DBI-3204, dinactin, dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan, ethiprole, ethofenprox, fenazaquin, flumite, MTI- 800, fenpyroximate, fluacrypyrim, flubenzimine, flubrocythrinate, flufenzine, flufenprox, fluproxyfen, halofenprox, hydra
  • Biological agents Bacillus thuringiensis ssp aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, virus and fungi.
  • Bactericides chlortetracycline, oxytetracycline, streptomycin.
  • Another aspect of invention is related to the use of a compound of formula I or of a preferred individual compound as above-defined, of a composition comprising at least one compound of formula I or at least one preferred individual compound as above-defined, or of a fungicidal or insecticidal mixture comprising at least one compound of formula I or at least one preferred individual compound as above-defined, in admixture with other fungicides or insecticides as described above, for controlling or preventing infestation of plants, e.g. useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living materials by insects or by phytopathogenic microorganisms, preferably fungal organisms.
  • useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living materials by insects or by phytopathogenic microorganisms, preferably fungal organisms.
  • a further aspect of invention is related to a method of controlling or preventing an infestation of plants, e.g. useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or of non-living materials by insects or by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, which comprises the application of a compound of formula I or of a preferred individual compound as above- defined as active ingredient to the plants, to parts of the plants or to the locus thereof, to the propagation material thereof, or to any part of the non-living materials.
  • Controlling or preventing means reducing infestation by insects or by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, to such a level that an improvement is demonstrated.
  • a preferred method of controlling or preventing an infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, or insects which comprises the application of a compound of formula I, or an agrochemical composition which contains at least one of said compounds, is foliar application.
  • the frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen or insect.
  • the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field.
  • the compounds of formula I may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
  • a formulation e.g. a composition containing the compound of formula I, and, if desired, a solid or liquid adjuvant or monomers for encapsulating the compound of formula I, may be prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface active compounds (surfactants).
  • extenders for example solvents, solid carriers and, optionally, surface active compounds (surfactants).
  • Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 10g to 1 kg a.i./ha, most preferably from 20g to 600g a.i./ha.
  • convenient dosages are from 10mg to 1g of active substance per kg of seeds.
  • rates of 0.001 to 50 g of a compound of formula I per kg of seed preferably from 0.01 to 10g per kg of seed are generally sufficient.
  • compositions of the invention may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK
  • compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects).
  • appropriate formulation inerts diiluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects.
  • conventional slow release formulations may be employed where long lasting efficacy is intended.
  • Particularly formulations to be applied in spraying forms such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g.
  • a seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds.
  • suitable seed dressing formulation form e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds.
  • seed dressing formulations are known in the art.
  • Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g. as slow release capsules or microcapsules.
  • the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of at least the compound of formula I together with component (B) and (C), and optionally other active agents, particularly microbiocides or conservatives or the like.
  • Concentrated forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent.
  • Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent.
  • commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations.
  • an activating reagent such as POCI 3 , PCI 3 , COCI 2 , PhS0 2 CI, Me 2 NS0 2 CI, (CF 3 CO) 2 0 or (MeO)
  • Scheme 1 b Compounds of formula (I) can be prepared by known methods from reacting an amino derivative of formula (IV), wherein R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are as defined for a compound of formula (I) and R' is defined as hydrogen or C0 2 tBu, with an orthoamide HC(OR z ) 2 -N(R )(R 2 ) of formula (V), wherein R-i and R 2 are as defined for a compound of formula (I) and R z is alkyl, in the presence of an acid.
  • a metal or metalloid group
  • a metal e.g. palladium
  • alkyllithium or alkymagnesium so as to perform a metal halogen exchange or trans-metalation followed by the introduction of an electrophile of formula (XI), wherein R 5d is as defined for a compound of formula (I) and T is an aldehyde or activated carboxylic acid derivative (i.e. acyl chloride, ester, acid anhydride or carboxamide).
  • R 5d is as defined for a compound of formula (I) and T is an aldehyde or activated carboxylic acid derivative (i.e. acyl chloride, ester, acid anhydride or carboxamide).
  • a compound of formula (le), wherein R , R 2 , R 3 , R 4 , R 6 , R 7 and R 8 are as defined for a compound of formula (I) and R 5ea is selected from aryl, heteroaryl, carbocyclic, heterocylic or alkyl groups and R 5eb is selected from hydrogen or alkyl, can be obtained from a compound of formula (VI), wherein R , R 2 , R 3 , R 4 , R 6 , R 7 and R 8 are as defined herein for a compound of formula (I) and X" is a halogen (e.g.
  • a compound of formula (IV), that is a compound of formula (IV) wherein R'is Hydrogen or Ac, can be prepared from a compound of formula (XVI), wherein R 5 , R 6 , R 7 , and R 8 are as defined for a compound of formula (IV), and an N-acyl amino ketone of formula (XVII), wherein R 3 is as defined herein for a compound of formula (I), via heating in the presence of base in aquous media followed by acidification and additional heating.
  • Compounds of formula (XVI) are known to be commercially available or can be made by known methods from known compounds. For examples, see: Wang, S. H. et al Med. Chem. Res. (2014), 23, 2161-2168
  • Compounds of formula (XVIII) are known or are commercially available.
  • Scheme 12 A compound of formula ( ⁇ '), wherein R 3 , R 4 , R 6 , R 7 and R 8 are as defined for a compound of formula (I), R is defined as hydrogen or C0 2 tBu and X'" is CN, CH 2 OH, CHO, C(0)Me, C0 2 Me, C0 2 Et, or a metal or metalloid (i.e.
  • boronic ester, boronic acid, tri-alkylstannane can be prepared from a compound of formula (XIX), wherein R 3 , R 4 , R 6 , R 7 and R 8 are as defined for a compound of formula (I), and X' is selected from CI, Br, or I, via treatment with an organometallic reagent (e.g. alkyllithium or alkymagnesium) followed by the introduction of an electrophile, such as an aldehyde, or an activated carboxylic acid derivative (i.e. acyl chloride, ester, acid anhydride or carboxamide), or via introduction of a Pd catalyst and a organometal or organometaloid (i.e. boronic ester, tri-alkylstannane chloride, or CuCN).
  • organometallic reagent e.g. alkyllithium or alkymagnesium
  • an electrophile such as an aldehyde, or an activated carboxylic
  • a compound of formula (XX) can be prepared from an amino compound of formula (XIX"), wherein R 3 , R 4 , R 6 , R 7 and R 8 are as defined for a compound of formula (I), X" is CI, Br, I, CN, CH 2 OH, CHO, C(0)Me, C0 2 Me, C0 2 Et, or a metal or metalloid (i.e.
  • an activating reagent such as POCI 3 , PCI 3 , COCI 2 , PhS0 2 CI, Me 2 NS0 2 CI, (CF 3 CO) 2 0 or (MeO) 2 S0 2 and then introducing a compound of formula (XIX").
  • a compound of formula (XX) can be prepared from an amino compound of formula (XIX"), wherein R 3 , R 4 , R 6 , R 7 and R 8 are as defined for a compound of formula (I), X" is CI, Br, I, CN, CH 2 OH, CHO, C(0)Me, C0 2 Me, C0 2 Et, or a metal or metalloid (i.e.
  • boronic ester, boronic acid, tri-alkylstannane) and R is defined as hydrogen or C0 2 tBu via a reaction with an orthoamide HC(OR z ) 2 -N(R )(R 2 ) of formula (V), wherein R-i and R 2 are as defined for a compound of formula (I) and R z is alkyl, in the presence of an acid.
  • a compound of formula (XIX) is selected from a compound of formula (XIX) or compound of formula ( ⁇ ').
  • Wettable powders a) b) c) active ingredient [compound of formula (I)] 25 % 50 % 75 % sodium lignosulfonate 5 % 5 %
  • the active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
  • Powders for drv seed treatment a) b) c) active ingredient [compound of formula (1)] 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 % -
  • the active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
  • Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water. Dusts a) b) c)
  • Active ingredient [compound of formula (I)] 5 % 6 % 4 % talcum 95 %
  • Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
  • the active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • polyethylene glycol (mol. wt. 200) 3 %
  • the finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner. Suspension concentrate
  • nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
  • silicone oil (in the form of a 75 % emulsion in water) 1 %
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • 28 parts of a combination of the compound of formula I are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8: 1 ).
  • This mixture is emulsified in a mixture of 1 .2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51 .6 parts of water until the desired particle size is achieved.
  • To this emulsion a mixture of 2.8 parts 1 ,6- diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
  • reaction mixture was diluted with water and extracted with ethyl acetate.
  • organic phases were dried over magnesium sulfate, filtered, concentrated and purified by chromatography (silica gel, heptane/ethyl acetate gradient 0-100%) to give the title compound as yellow oil.
  • reaction mixture was then diluted with ethyl acetate, filtered, washed with water and brine, dried over magnesium sulfate, concentrated and purified by combiflash column chromatography (silica gel, heptane/ethyl acetate gradient 0-100%) to give the title compound as yellow oil.
  • N-Ethyl-N-methyl-N'-[8-[(E)-3-methoxyprop-1-enyl]-2-methyl-3-quinolyl]-formamidine (0.17g) was dissolved in methanol (3 mL) and hydrogenated using an H-Cube ® continuous-flow hydrogenation reactor via passage at 55°C with a flow of 1 mL minute and a pressure of 20 bar through a CatCarts® cartridge loaded with palladium 10% on carbon (0.02 g). The tubes were washed with methanol and the combined fractions were concentrated and the residue was purified by combiflash column chromatography (silica gel, heptane/ethyl acetate gradient 0-100%) to give the title compound as light yellow oil.
  • the pH of the reaction mixture was adjusted to pH 8 by addition of aqueous NaOH (2M) and the suspension was extracted with tert-butyl methyl ether. The organic layer was washed with brine, dried over MgS0 4 , and the solids removed by filtration. The solvent was removed at reduced pressure and the residue purified by flash chromatography over silica gel (cyclohexane/ethyl acetategradient from 0% - 40%) to give the title compound as a light brown amorphous solid.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

L'invention concerne des composés de formule (I) dans laquelle R1, R2, R3, R4, R5, R6, R7 et R8 sont tels que définis dans les revendications. L'invention concerne en outre des compositions contenant lesdits composés et leur utilisation en agriculture ou en horticulture pour prévenir l'infestation de végétaux par des micro-organismes phytopathogènes, de préférence des champignons. ou pour lutter contre ladite infestation.
PCT/EP2015/078542 2014-12-05 2015-12-03 Nouvelles quinolinylamidines fongicides WO2016087593A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018031434A1 (fr) * 2016-08-08 2018-02-15 Merck Patent Gmbh Antagonistes de tlr7/8 et leurs utilisations
EP3643175A1 (fr) 2018-10-24 2020-04-29 Basf Se Mélanges pesticides ternaires contenant du metyltetraprole et du fenpropimorphe
US11629134B2 (en) 2015-12-17 2023-04-18 Merck Patent Gmbh TLR7/8 antagonists and uses thereof

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11629134B2 (en) 2015-12-17 2023-04-18 Merck Patent Gmbh TLR7/8 antagonists and uses thereof
WO2018031434A1 (fr) * 2016-08-08 2018-02-15 Merck Patent Gmbh Antagonistes de tlr7/8 et leurs utilisations
US10947214B2 (en) 2016-08-08 2021-03-16 Merck Patent Gmbh TLR7/8 antagonists and uses thereof
AU2017311047B2 (en) * 2016-08-08 2021-07-22 Merck Patent Gmbh TLR7/8 antagonists and uses thereof
RU2758686C2 (ru) * 2016-08-08 2021-11-01 Мерк Патент Гмбх Антагонисты tlr7/8 и их применение
US11512069B2 (en) 2016-08-08 2022-11-29 Merck Patent Gmbh TLR7/8 antagonists and uses thereof
EP4198031A1 (fr) * 2016-08-08 2023-06-21 Merck Patent GmbH Antagonistes de tlr7/8 et leurs utilisations
EP3643175A1 (fr) 2018-10-24 2020-04-29 Basf Se Mélanges pesticides ternaires contenant du metyltetraprole et du fenpropimorphe

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