WO2014075873A1 - Microbiocidal pyrazole derivatives - Google Patents

Microbiocidal pyrazole derivatives Download PDF

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Publication number
WO2014075873A1
WO2014075873A1 PCT/EP2013/071984 EP2013071984W WO2014075873A1 WO 2014075873 A1 WO2014075873 A1 WO 2014075873A1 EP 2013071984 W EP2013071984 W EP 2013071984W WO 2014075873 A1 WO2014075873 A1 WO 2014075873A1
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formula
alkyl
compounds
hydrogen
independently
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PCT/EP2013/071984
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French (fr)
Inventor
Martin Pouliot
Fredrik Cederbaum
Sarah Sulzer-Mosse
Laura Quaranta
Werner Zambach
Clemens Lamberth
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Syngenta Participations Ag
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Publication of WO2014075873A1 publication Critical patent/WO2014075873A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • 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
    • C07D417/14—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 three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/10—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D498/20—Spiro-condensed systems

Definitions

  • the present invention relates to microbiocidal pyrazole derivatives, e.g. as active ingredients, which have microbiocidal activity, in particular fungicidal activity.
  • the invention also relates to preparation of these pyrazole derivatives, to pyrazole derivatives used as intermediates in the preparation of these pyrazole derivatives, to preparation of these intermediates, to agrochemical compositions which comprise at least one of the pyrazole derivatives, to preparation of these compositions and to use of the pyrazole derivatives or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, preferably fungi.
  • the present invention provides compounds of formula I:
  • G and G 2 are independently O or S;
  • T is CR 11 or N
  • Y 1 and Y 2 are independently CR 12 or N;
  • n 1 or 2;
  • p is 1 or 2, providing that when n is 2, p is 1 ;
  • R 1 and R 2 each independently are CrC 4 alkyl, C 3 -C 5 cycloalkyl or CrC 4 haloalkyl;
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently are hydrogen, halogen, cyano, Ci-C 4 alkyl, Ci-
  • R 10 is hydrogen, C 1 -C 4 alkyl, CrC ⁇ haloalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 - C 6 alkylaminocarbonyl, di-(C 2 -C 6 alkyl)aminocarbonyl or a 5- to 10-membered mono- or bicyclic, saturated, partially unsaturated or aromatic carbocyclic or heterocyclic ring system optionally containing 1 to 4 ring members selected from the group consisting of nitrogen, oxygen and sulfur;
  • R 11 is hydrogen, halogen or hydroxyl
  • R 12 is hydrogen, halogen or cyano
  • each R 13 independently is hydrogen, Ci-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 3 alkynyl, C 3 -
  • each R 14 independently is halogen, cyano, amino, nitro, hydroxyl, mercapto, C C 8 alkyl, C 2 - C 8 alkenyl, C 2 -C 8 alkynyl, C 3 -C 8 cycloalkyl, Cs-Cscycloalkyl-CrC ⁇ alkyl, Ca-Cscycloalkyl-C C 4 alkoxy, Cs-Cscycloalkyl-Cr alkylthio, CrCsalkoxy, C 3 -C 8 cycloalkoxy, CrCsalkenyloxy, C 2 -C 8 alkynyloxy, CrCsalkylthio, CrCsalkylsulfonyl, C-i-Csalkylsulfinyl, C 3 -C 8 cycloalkylthio, C 3 - Cscycloalkylsulfonyl, C 3 -C 8 cycloalkylsulfin
  • each R 15 independently is halogen, cyano, C-i-C 4 alkyl, C C 4 haloalkyl, CrC 4 alkoxy or d- C 4 haloalkoxy,
  • substituents are indicated as being optionally substituted, this means that they may or may not carry one or more identical or different substituents, e.g. one to five substituents, e.g. one to three substituents. Normally not more than three such optional substituents are present at the same time.
  • substituents are indicated as being substituted, e.g. alkyl, unless stated otherwise this includes those groups that are part of other groups, e.g. the alkyl in alkylthio.
  • halogen refers to fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
  • Alkyl substituents may be straight-chained or branched. Alkyl on its own or as part of another substituent is, depending upon the number of carbon atoms mentioned, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl and the isomers thereof, for example, iso- propyl, iso-butyl, sec-butyl, tert-butyl, iso-amyl or pivaloyl.
  • Alkenyl substituents can be in the form of straight or branched chains, and the alkenyl moieties, where appropriate, can be of either the (E)- or (Z)-configuration. Examples are vinyl and allyl.
  • the alkenyl groups are preferably C 2 -C 6 , more preferably C 2 -C 4 and most preferably C2-C3 alkenyl groups.
  • Alkynyl substituents can be in the form of straight or branched chains. Examples are ethynyl and propargyl.
  • the alkynyl groups are preferably C 2 -C 6 , more preferably C 2 -C 4 and most preferably C 2 -C 3 alkynyl groups.
  • Haloalkyl groups may contain one or more identical or different halogen atoms and, for example, may stand for CH 2 CI, CHCI 2 , CCI 3 , CH 2 F, CHF 2 , CF 3 , CF 3 CH 2 , CH 3 CF 2 , CF 3 CF 2 or
  • Haloalkenyl groups are alkenyl groups, respectively, which are substituted with one or more of the same or different halogen atoms and are, for example, 2,2-difluorovinyl or 1 ,2- dichloro-2-fluoro-vinyl.
  • Haloalkynyl groups are alkynyl groups, respectively, which are substituted with one or more of the same or different halogen atoms and are, for example, 1-chloro-prop-2-ynyl.
  • Alkoxy means a radical -OR, where R is alkyl, e.g. as defined above.
  • Alkoxy groups include, but are not limited to, methoxy, ethoxy, 1 -methylethoxy, propoxy, butoxy, 1 - methylpropoxy and 2-methylpropoxy.
  • Cyano means a -CN group.
  • Amino means an NH 2 group.
  • Hydroxyl or hydroxy stands for a -OH group.
  • Aryl means a ring system which may be mono-, bi- or tricyclic. Examples of such rings include phenyl, naphthalenyl, anthracenyl, indenyl or phenanthrenyl. A preferred aryl group is phenyl.
  • Heteroaryl stands for aromatic ring systems comprising mono-, bi- or tricyclic systems wherein at least one oxygen, nitrogen or sulfur atom is present as a ring member.
  • Monocyclic and bicyclic aromatic ring systems are preferred, monocyclic ring systems are more preferred.
  • monocyclic heteoraryl may be a 5- to 7-membered aromatic ring containing one to three heteroatoms selected from oxygen, nitrogen and sulfur, more preferably selected from nitrogen and sulfur.
  • Bicyclic heteroaryl may be a 9- to 1 1-membered bicyclic ring containing one to five heteroatoms, preferably one to three heteroatoms, selected from oxygen, nitrogen and sulfur.
  • Examples are furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl,
  • Heteroaryl rings do not contain adjacent oxygen ring atoms, adjacent sulfur ring atoms or adjacent oxygen and sulfur ring atoms.
  • a link to a heteroaryl group can be via a carbon atom or via a nitrogen atom.
  • Carbocyclic ring system includes aryl and in addition their saturated or partially unsaturated analogues.
  • Heterocyclyl and heterocyclic ring system are used interchangeably and unless otherwise stated refer to include heteroaryl and in addition their saturated or partially unsaturated analogues.
  • the different rings of bi- or tricyclic heterocyclic ring systems may be linked via one atom belonging to two different rings (spiro), via two adjacent ring atoms belonging to two different rings (annelated) or via two different, not adjacent ring atoms belonging to two different rings (bridged).
  • asymmetric carbon atoms in a compound of formula I means that the compounds may occur in optically isomeric forms, i.e. enantiomeric or diastereomeric forms. Also atropisomers may occur as a result of restricted rotation about a single bond.
  • Formula I is intended to include all those possible isomeric forms and mixtures thereof.
  • the present invention includes all those possible isomeric forms and mixtures thereof for a compound of formula I.
  • formula I is intended to include all possible tautomers.
  • the present invention includes all possible tautomeric forms for a compound of formula I.
  • the compounds of formula I according to the invention are in free form, in oxidized form as a N-oxide or in salt form, e.g. an agronomically usable salt form.
  • N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book "Heterocyclic N- oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
  • G 1 and G 2 are independently 0 or S.
  • G 1 is preferably O.
  • G 2 is preferably S.
  • T is CR 11 or N, preferably CH or N, more preferably CH.
  • Y 1 and Y 2 are independently CR 12 or N.
  • Y 1 is preferably CH or N, more preferably N.
  • Y 2 is preferably CH or N; more preferably CH.
  • n 1 or 2, preferably 2.
  • p is 1 or 2, providing that when n is 2, p is 1 , preferably p is 1.
  • p is 1 and n is 2.
  • R 1 and R 2 each independently are Ci-C 4 alkyl, C 3 -C 5 cycloalkyl or Ci-C 4 haloalkyl.
  • R 1 and R 2 are each independently methyl or halomethyl, more preferably methyl, difluoromethyl or trifluoromethyl.
  • R 1 is difluoromethyl or trifluoromethyl.
  • R 2 is methyl or difluoromethyl. In one group of compounds R 1 is trifluoromethyl and R 2 is methyl. In another group of compounds R 1 and R 2 are both difluoromethyl.
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently are hydrogen, halogen, cyano, C C 4 alkyl, C C 4 alkoxy, C 3 -C 5 cycloalkyl, C-
  • R 3 is carboxyl, C C 4 alkoxycarbonyl, C 1 -C 4 haloalkoxycarbonyl, aminocarbonyl, (Cr ⁇ alkyljaminocarbonyl, (C 1 -C 4 haloalkyl)aminocarbonyl, (C
  • Ci-C 4 haloalkoxycarbonyl aminocarbonyl, (Ci-C 4 alkyl)aminocarbonyl, (Ci- C 4 haloalkyl)aminocarbonyl, (CrC 4 alkyl) 2 aminocarbonyl or (Ci-C 4 haloalkyl) 2 aminocarbonyl and preferably carboxyl or Ci-C 4 alkoxycarbonyl, and R 3 , R 5 , R 6 , R 7 and R 8 are hydrogen.
  • R 10 is hydrogen, Ci-C alkyl, Ci-C 4 haloalkyl, C 2 -C 6 alkylcarbonyl, or C 2 - C 6 alkoxycarbonyl; more preferably hydrogen.
  • R 11 is hydrogen, halogen or hydroxy; preferably hydrogen or hydroxy, more preferably hydrogen.
  • R 12 is hydrogen, halogen or cyano; preferably hydrogen or cyano, more preferably hydrogen.
  • each R 13 independently is hydrogen, CrC 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl,
  • each R 14 independently is halogen, cyano, Ci-C 6 alkyl, C 3 -C 7 cycloalkyl, C C 6 alkoxy, C Csalkylthio or C-rC 6 alkylsulfonyl wherein alkyl, cycloalkyl and alkoxy are optionally substituted by halogen; preferably halogen, C -C 4 alkyl or C C 4 alkoxy wherein alkyl and alkoxy are optionally substituted by halogen; more preferably halogen, C-rC 4 alkyl or C-p C 4 alkoxy and most preferably fluoro, Ci-C 4 alkyl or C 1 -C 4 alkoxy.
  • each R 15 independently is fluoro, chloro, methyl or methoxy.
  • the compound of formula I is a compound wherein:
  • G 2 is S
  • T CH or N
  • Y 1 and Y 2 are independently CH or N;
  • n 1 or 2;
  • p is 1 or 2, providing that when n is 2, p is 1 ;
  • R 1 and R 2 each independently are methyl or halomethyl
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently are hydrogen, halogen, methyl, thiomethyl or halomethyl;
  • R 10 is hydrogen, Ci-C 4 alkyl, Ci-C haloalkyl, C 2 -C 6 alkylcarbonyl, or C 2 -C 6 alkoxycarbonyl,
  • each R 14 independently from each other is halogen, Ci-C 8 alkyl, Ci-C 8 alkoxy,
  • the compound of formula I is a compound wherein:
  • G 2 is S
  • T CH or N
  • Y 1 and Y 2 are independently CH or N;
  • n 1 or 2;
  • p is 1 or 2, providing that when n is 2, p is 1 ;
  • R 1 and R 2 each independently are methyl or halomethyl
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently are hydrogen, halogen, methyl, thiomethyl or halomethyl;
  • R 10 is hydrogen
  • Each R 13 independently from each other, is hydrogen, C C 6 alkyl, Ci-C 6 haloalkyl, each R 14 independently from each other is halogen, d-Cealkyl, C ⁇ Caalkoxy,
  • the compound of formula I is a compound wherein G 1 , is O, G 2 is S, G 3 is O, Y 1 is N, and Y 2 is CH.
  • the compound of formula I is a compound wherein R 1 and R 2 each independently are methyl, difluoromethyl or trifluoromethyl and R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each
  • each R 13 independently is hydrogen, CrC 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, CrC 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl; each R 14 independently is halogen, d-C 6 alkyl, C C 6 alkoxy, Ci-C 6 alkylthio, wherein alkyl and alkoxy are optionally substituted by halogen.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , G 1 , G 2 , T, Y 1 and Y 2 have the definitions as described for formula I.
  • R 1 , R 2 R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , G 1 , G 2 , T, Y 1 and Y 2 have the definitions as described for formula I.
  • R 1 , R 2 R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , G 1 , G 2 , T, Y 1 and Y 2 have the definitions as described for formula I.
  • the invention also relates to compounds of formula l-a, formula l-b and formula l-c as shown above.
  • the invention also relates to compounds of formula l-d:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , G 2 , Y 1 and Y 2 have the definitions as described for formula I.
  • Preferred definitions of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 0 , G 2 , Y 1 and Y 2 are as defined for formula I.
  • the invention also relates to compounds of formula l-e:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 have the definitions as described for formula I.
  • Preferred definitions of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are as defined for formula I.
  • the invention also relates to compounds of formula l-f:
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , G 1 , G 2 , T, Y 1 , Y 2 , n and p have the definition as described for formula I.
  • Preferred definitions of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , G 1 , G 2 , T, Y 1 , Y 2 , n and p are as defined for formula I.
  • the invention also relates to compounds of formula l-g:
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , G 1 , G 2 , T, Y 1 , Y 2 , n and p have the definitions as described for formula I.
  • Preferred definitions of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , G 1 , G 2 , T, Y 1 , Y 2 , n and p are as defined for formula I.
  • the invention includes compounds of formula II:
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , G 2 , T, Y 1 , Y 2 , n and p are as defined for a compound of formula I and E is hydrogen or E 1 , wherein E 1 is a protecting group, such as alkylcarbonyl, benzyl or alkoxycarbonyl, e.g. C C 4 alkylcarbonyl, benzyl or C-rC 4 alkoxycarbonyl, in particular acetyl, benzyl or tert-butoxycarbonyl.
  • E 1 is a protecting group, such as alkylcarbonyl, benzyl or alkoxycarbonyl, e.g. C C 4 alkylcarbonyl, benzyl or C-rC 4 alkoxycarbonyl, in particular acetyl, benzyl or tert-butoxycarbonyl.
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , G 2 , T, Y 1 , Y 2 , n and p are as defined for formula I.
  • the compounds of formula I wherein R1 , R2, R3, R4, R5, R6, R7, R8, R9, R10, G1 , G2, T, Y1 , Y2, n and p are as defined for formula I can be obtained by transformation of a compound of formula IV, wherein the group M is defined above and R17 is hydroxy, halogen, preferably fluoro, chloro or bromo, or alkoxy, such as methoxy or ethoxy, with a compound of formula III, wherein R3, R4, R5, R6, R7, R8, R9, R10, G2, T, Y1 , Y2, n and p are as defined for formula I, and a base or an activating agent. This is shown in Scheme 1.
  • the compounds of formula VI wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , G 2 , T, Y 1 , Y 2 , n and p are as defined for formula I and E is hydrogen or E 1 , can be obtained by transformation of a compound of formula VII, wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , G 2 , T, Y 1 , Y 2 , n and p are as defined for formula I and E is hydrogen or E 1 , with a compound of formula VIII, wherein R 9 and R 10 are as defined for formula I, and hydroxylamine and sodium hypochlorite.
  • compounds of formula VI wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , G 2 , T, Y 1 , Y 2 , n and p are as defined for formula I and E is hydrogen or E 1 , can be obtained stepwise by transformation of a compound of formula IX, wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , G 2 , T, Y 1 , Y 2 , n and p are as defined for formula I and E is hydrogen or E 1 , with a compound of formula VIII, wherein R 9 and R 10 are as defined for formula I, and an oxidant such as sodium hypochlorite, /V-chlorosuccinimide or diacetoxyiodobenzene.
  • an oxidant such as sodium hypochlorite, /V-chlorosuccinimide or diacetoxyiodobenzene.
  • R 18 is In, MgCI, MgBr, Sn(R 19 ) 3 , ZnCI, ZnBr or B(OR 19 ) 2 , wherein either R 19 is independently from each other hydrogen, C Ce alkyl or wherein two R 19 together can form a C 3 -C 8 cycloalkyl, with a compound of formula XI, wherein R 10 is as defined under formula I and Hal is a halogen, preferably chloro, bromo or iodo, and a catalyst, such as
  • the compounds of formula VI wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , T, n and p are as defined for formula I, G2 is S, Y1 is N, Y2 is CH, and E is hydrogen or E 1 , can be obtained by transformation of a compound of formula XII, wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , n and p are as defined for formula I and E is hydrogen or E 1 , with a compound of formula XIII, wherein R 9 and R 10 are as defined for formula I and Hal is a halogen, preferably chloro or bromo, and a base.
  • This route is shown in Scheme 5.
  • the compounds of formula XIII, wherein R 9 and R 10 are as defined for formula I and Hal is a halogen, preferably chloro or bromo can be obtained by transformation of a compound of formula XIV, wherein each Hal independently from each other is a halogen, preferably chloro or bromo, with a compound of formula XIII, wherein R 9 and R 10 are as defined for formula I and Hal is a halogen, preferably chloro or bromo, and a base. This route is shown in Scheme 6.
  • novel compounds of formula I have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.
  • 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 novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and may be used for protecting numerous cultivated plants.
  • the compounds of formula I can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later e.g. from phytopathogenic microorganisms.
  • compositions 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.
  • the compounds according to present invention can be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage, in hygiene management.
  • the invention could be used to protect non-living materials from fungal attack, e.g. lumber, wall boards and paint.
  • the compounds of formula I are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Alternaria spp.), Basidiomycetes (e.g. Corticium spp., Ceratobasidium spp., Waitea spp., Thanatephorus spp., Rhizoctonia spp., Hemileia spp., Puccinia spp., Phakopsora spp., Ustilago spp., Tilletia spp.), Ascomycetes (e.g.
  • Venturia spp. Blumeria spp., Erysiphe spp., Podosphaera spp., Uncinula spp., Monilinia spp., Sclerotinia spp., Colletotrichum spp., Glomerella spp., Fusarium spp.,
  • Gibberella spp. Monographella spp., Phaeosphaeria spp., Mycosphaerella spp., Cercospora spp., Pyrenophora spp., Rhynchosporium spp., Magnaporthe spp., Gaeumannomyces spp., Oculimacula spp., Ramularia spp., Botryotinia spp.) and Oomycetes (e.g. Phytophthora spp., Pythium spp., Plasmopara spp., Peronospora spp., Pseudoperonospora spp. Bremia spp).
  • novel compounds of formula I are effective against phytopathogenic gram negative and gram positive bacteria (e.g.
  • Xanthomonas spp Pseudomonas spp, Erwinia amylovora, Ralstonia spp.
  • viruses e.g. tobacco mosaic virus
  • target crops and/or 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)
  • the useful plants and / or target crops in accordance with the invention include conventional as well as genetically enhanced or engineered varieties such as, for example, insect resistant (e.g. Bt. and VIP varieties) as well as disease resistant, herbicide tolerant (e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®) and nematode tolerant varieties.
  • suitable genetically enhanced or engineered crop varieties include the Stoneville 5599BR cotton and Stoneville 4892BR cotton varieties.
  • useful plants and/or “target crops” 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
  • useful plants and/or “target crops” 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.
  • useful plants and/or target crops 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 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).
  • PRPs pathogenesis-related proteins
  • 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-0 353 191.
  • 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.
  • locus of a plant as used herein is intended to embrace the place on which the plants are growing, where the plant propagation materials of the plants are sown or where the plant propagation materials of the plants will be placed into the soil.
  • 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. 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 may be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they may be conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
  • Suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890.
  • the compounds of formula I are normally used in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g. fertilizers or micronutrient donors or other preparations, which influence the growth of plants.
  • They can also be selective herbicides or non-selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
  • the compounds of formula I may be used in the form of (fungicidal) compositions for controlling or protecting against phytopathogenic microorganisms, comprising as active ingredient at least one compound of formula I or of at least one preferred individual compound as above-defined, in free form or in agrochemically usable salt form, and at least one of the above-mentioned adjuvants.
  • the invention provides a composition, preferably a fungicidal composition, comprising at least one compound formula I an agriculturally acceptable carrier and optionally an adjuvant.
  • An agricultural acceptable carrier is for example a carrier that is suitable for agricultural use.
  • Agricultural carriers are well known in the art.
  • said composition may comprise at least one or more pesticidally active compounds, for example an additional fungicidal active ingredient in addition to the compound of formula I.
  • the compound of formula (I) may be the sole active ingredient of a composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate.
  • An additional active ingredient may, in some cases, result in unexpected synergistic activities.
  • suitable additional active ingredients include the following: Azoxystrobin (131860-33-8), Dimoxystrobin (149961-52-4), Enestrobin (238410-1 1-2), Fluoxastrobin (193740-76-0),
  • Spiroxamine (118134-30-8), Isopyrazam (881685-58-1 ), Sedaxane (874967-67-6), Bixafen (581809-46-3), Penthiopyrad (183675-82-3), Fluxapyroxad (907204-31 -3), Boscalid (188425- 85-6), Penflufen (494793-67-8), Fluopyram (658066-35-4), Mandipropamid (374726-62-2), Benthiavalicarb (413615-35-7), Dimethomorph (1 10488-70-5), Chlorothalonil (1897-45-6), Fluazinam (79622-59-6), Dithianon (3347-22-6), Metrafenone (220899-03-6), Tricyclazole (41814-78-2), Mefenoxam (70630-17-0), Metalaxyl (57837-19-1 ), Acibenzolar (126448-41 -7) (Acibenzolar-S-methyl (12
  • 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 mixture comprising at least one compound of formula I or at least one preferred individual compound as above-defined, in admixture with other fungicides, 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 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 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
  • phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms which comprises the application of a compound of formula I or of a preferred individual compound as above-defined as active ingredient to the plants, to parts of the plants or to the locus thereof, to the propagation material thereof, or to any part of the non-living materials.
  • Controlling or preventing means reducing infestation by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, to such a level that an improvement is demonstrated.
  • a preferred method of controlling or preventing an infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, 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.
  • 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
  • the agrochemical formulations and/or compositions 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 10g to 1 kg a.i./ha, most preferably from 20g to 600g a.i./ha.
  • convenient dosages are from 10mg to 1 g of active substance per kg of seeds.
  • Triethylamine (9.72g) was added at 0-5°C to a solution of 2-(4-piperidyl)thiazole-4- carbaldehyde dihydrochloride (8.0) in dichloromethane (100ml_).
  • Acetylchloride (2.80g) was added at 0-5°C, the reaction mixture was warmed up and stirred for 16h at 25°C.
  • the reaction mixture was poured onto sodium bicarbonate solution (300ml_; 20% in water) and extracted with dichloromethane. The combined organic phases were washed with brine dried over magnesiumsulfate, filtered and concentrated. The residue was purified by
  • Table 1 illustrates examples of individual compounds of formula I according to the invention.
  • R 1 , R 2 , R 13 , G 2 , T, Y 1 and Y 2 are as defined in Table 1.
  • R 1 , R 2 , R 13 , G 2 , T, Y 1 and Y 2 are as defined in Table 1 ah 216 compounds of formula (I. ah):
  • R 1 , R 2 , R 3 , G 2 , T, Y and Y 2 are as defined in Table 1.
  • R 1 , R 2 , R 13 , G 2 , T, Y 1 and Y 2 are as defined in Table 1.
  • LC/MS Liquid Chromatography Mass Spectroscopy and the description of the apparatus and the method is:
  • Spectra were recorded on a Mass Spectrometer from Waters (SQD or ZQ Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range: 30-60 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 350°C, Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment and diode-array detector. Solvent degasser, binary pump, heated column compartment and diode-array detector.
  • Tomato leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf disks are inoculated with a spore suspension of the fungus 1 day after application.
  • the inoculated leaf disks are incubated at 16°C and 75% rh under a light regime of 24 h darkness followed by 12 h light /
  • Phvtoohthora infestans I potato / preventative (potato late blight " ) 2-week old potato plants cv. Bintje are sprayed in a spray chamber with the formulated test compound diluted in water.
  • the test plants are inoculated by spraying them with a sporangia suspension 2 days after application.
  • the inoculated test plants are incubated at 18° C with 14 h light/day and 100 % rh in a growth chamber and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (5 - 7 days after application).
  • Compounds (from table 2) 1 , 6 , 7 , 12 and 22 at 200 ppm give at least 80% disease control in this test when compared to untreated control plants under the same conditions, which show extensive disease development.
  • 2-week old potato plants cv. Bintje are inoculated by spraying them with a sporangia suspension one day before application.
  • the inoculated plants are sprayed in a spray chamber with the formulated test compound diluted in water.
  • the inoculated test plants are incubated at 18° C with 14 h light/day and 100 % rh in a growth chamber and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (3 - 4 days after application).
  • Compounds (from table 2) 1 , 7 , 12 and 22 at 200 ppm give at least 80% disease control in this test when compared to untreated control plants under the same conditions, which show extensive disease development.
  • 2-week old potato plants cv. Bintje are sprayed in a spray chamber with the formulated test compound diluted in water.
  • the test plants are inoculated by spraying them with a sporangia suspension 6 days after application.
  • the inoculated test plants are incubated at 18° C with 14 h light/day and 100 % rh in a growth chamber and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (9 - 1 1 days after application).
  • Compounds (from table 2) 1 , 6 , 7 , 12 and 22 at 200 ppm give at least 80% disease control in this test when compared to untreated control plants under the same conditions, which show extensive disease development.
  • Plasmopara viticola I grape / leaf disc preventative (grape downy mildew)
  • Grape vine leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf disks are inoculated with a spore suspension of the fungus 1 day after application.
  • the inoculated leaf disks are incubated at 19°C and 80% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (6 - 8 days after application).
  • 5-week old grape seedlings cv. Gutedel are sprayed in a spray chamber with the formulated test compound diluted in water.
  • the test plants plants are inoculated by spraying a sporangia suspension on their lower leaf surface one day after application.
  • the inoculated test plants are incubated at 22° C and 100% rh in a greenhouse and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (6 - 8 days after application).
  • Compounds (from table 2) 1 , 6 , 7 , 12 and 22 at 200 ppm give at least 80% disease control in this test when compared to untreated control plants under the same conditions, which show extensive disease development.
  • Plasmopara viticola I grape / curative (grape downy mildew)
  • 5-week-old grape seedlings cv. Gutedel are inoculated by spraying a sporangia suspension on their lower leaf surface one day before application.
  • the inoculated grape plants are sprayed in a spray chamber with the formulated test compound diluted in water.
  • the inoculated test plants are incubated at 22° C and 100% rh in a greenhouse and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (4 - 6 days after application).
  • 5-week old grape seedlings cv. Gutedel are sprayed in a spray chamber with the formulated test compound diluted in water.
  • the test plants are inoculated by spraying a sporangia suspension on their lower leaf surface 6 days after application.
  • the inoculated test plants are incubated at 22° C and 100% rh in a greenhouse and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (1 1 - 13 days after application).
  • Mycelia fragments and oospores 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 test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal mycelia/spore mixture is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 2-3 days after application.
  • DMSO DMSO
  • Compounds (from table 2) 22 , 28 , 30 , 33 , 39 and 40 at 20 ppm give at least 80% disease control in this test when compared to untreated control under the same conditions, which show extensive disease development.

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Abstract

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

Description

Microbiocidal Pyrazole Derivatives
The present invention relates to microbiocidal pyrazole derivatives, e.g. as active ingredients, which have microbiocidal activity, in particular fungicidal activity. The invention also relates to preparation of these pyrazole derivatives, to pyrazole derivatives used as intermediates in the preparation of these pyrazole derivatives, to preparation of these intermediates, to agrochemical compositions which comprise at least one of the pyrazole derivatives, to preparation of these compositions and to use of the pyrazole derivatives or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, preferably fungi.
Certain compounds for use as fungicides are described in WO 2007/014290, WO 2008/013622, WO 2008/013925, WO 2008/091580, WO 2008/091594 and WO
2009/055514.
The present invention provides compounds of formula I:
Figure imgf000002_0001
G and G2 are independently O or S;
T is CR11 or N;
Y1 and Y2 are independently CR12 or N;
n is 1 or 2;
p is 1 or 2, providing that when n is 2, p is 1 ;
R1 and R2 each independently are CrC4alkyl, C3-C5cycloalkyl or CrC4haloalkyl;
R3, R4, R5, R6, R7 and R8 each independently are hydrogen, halogen, cyano, Ci-C4alkyl, Ci-
C4alkoxy, C3-C5cycloalkyl, Ci-C4haloalkyl, or Ci-C4thioalkyl;
R9 is a 5- to 1 1-membered mono-, bi- or tricyclic, saturated or partially unsaturated carbocyclic or heterocyclic ring system, containing at least one ring member selected from the group consisting of C(=NOR13), C(=NR13), C(=NN(R13)2) or C(=NNR13S02R13), and optionally containing one or more ring member(s) selected from the group consisting of O, S, N, C(=0), (C=S), S(O), or S(0)2, said carbocyclic or heterocyclic ring system being further optionally substituted by one or more R14;
R10 is hydrogen, C1-C4alkyl, CrC^haloalkyl, C2-C6alkylcarbonyl, C2-C6alkoxycarbonyl, C2- C6alkylaminocarbonyl, di-(C2-C6alkyl)aminocarbonyl or a 5- to 10-membered mono- or bicyclic, saturated, partially unsaturated or aromatic carbocyclic or heterocyclic ring system optionally containing 1 to 4 ring members selected from the group consisting of nitrogen, oxygen and sulfur;
R11 is hydrogen, halogen or hydroxyl;
R12 is hydrogen, halogen or cyano;
each R13 independently is hydrogen, Ci-C6alkyl, C2-C6alkenyl, C2-C3alkynyl, C3-
C6cycloalkyl, CrC6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, C2- C6alkylcarbonyl, C2-C6alkoxycarbonyl, C2-C6alkylaminocarbonyl, or di-(C2- C6alkyl)aminocarbonyl or is a 5- to 10-membered aromatic, saturated or partially saturated monocyclic or fused bicyclic ring system optionally containing 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, where the ring system is directly attached to the rest of the molecule or via a Ci-C4alkyl, C2-C4alkenyl, C2-C4alkynyl, d.
C4alkoxy or C _C4alklythio group, and wherein the ring system is optionally substituted by one or more R15 and does not contain more than two oxygen atoms and not more than two sulfur atoms;
each R14 independently is halogen, cyano, amino, nitro, hydroxyl, mercapto, C C8alkyl, C2- C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, Cs-Cscycloalkyl-CrC^alkyl, Ca-Cscycloalkyl-C C4alkoxy, Cs-Cscycloalkyl-Cr alkylthio, CrCsalkoxy, C3-C8cycloalkoxy, CrCsalkenyloxy, C2-C8alkynyloxy, CrCsalkylthio, CrCsalkylsulfonyl, C-i-Csalkylsulfinyl, C3-C8cycloalkylthio, C3- Cscycloalkylsulfonyl, C3-C8cycloalkylsulfinyl, aryl, aryloxy, arylthio, arylsulfonyl, arylsulfinyl, aryl-Ci-C4alkyl, aryl-Ci-C4alkoxy, aryl-Ci-C4alkylthio, heterocyclyl, heterocycyl-CrC4alkyl, heterocycyl-Ci-C4alkoxy, heterocycyl-C C4alkylthio, NH(CrC8alkyl), N(Ci-C8alkyl)2, Ci- C4alkylcarbonyl, C3-C8cycloalkylcarbonyl, C2-C8alkenylcarbonyl, C2-C8alkynylcarbonyl, wherein alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, alkenyloxy, alkynyloxy and cycloalkoxy are optionally substituted by halogen, and wherein aryl and heterocyclyl are optionally substituted by one or more R15;
each R15 independently is halogen, cyano, C-i-C4alkyl, C C4haloalkyl, CrC4alkoxy or d- C4haloalkoxy,
or a salt or a N-oxide thereof.
Where substituents are indicated as being optionally substituted, this means that they may or may not carry one or more identical or different substituents, e.g. one to five substituents, e.g. one to three substituents. Normally not more than three such optional substituents are present at the same time. Where a group is indicated as being substituted, e.g. alkyl, unless stated otherwise this includes those groups that are part of other groups, e.g. the alkyl in alkylthio.
The term "halogen" refers to fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
Alkyl substituents may be straight-chained or branched. Alkyl on its own or as part of another substituent is, depending upon the number of carbon atoms mentioned, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl and the isomers thereof, for example, iso- propyl, iso-butyl, sec-butyl, tert-butyl, iso-amyl or pivaloyl.
Alkenyl substituents can be in the form of straight or branched chains, and the alkenyl moieties, where appropriate, can be of either the (E)- or (Z)-configuration. Examples are vinyl and allyl. The alkenyl groups are preferably C2-C6, more preferably C2-C4 and most preferably C2-C3 alkenyl groups.
Alkynyl substituents can be in the form of straight or branched chains. Examples are ethynyl and propargyl. The alkynyl groups are preferably C2-C6, more preferably C2-C4 and most preferably C2-C3 alkynyl groups.
Haloalkyl groups may contain one or more identical or different halogen atoms and, for example, may stand for CH2CI, CHCI2, CCI3, CH2F, CHF2, CF3, CF3CH2, CH3CF2, CF3CF2 or
Haloalkenyl groups are alkenyl groups, respectively, which are substituted with one or more of the same or different halogen atoms and are, for example, 2,2-difluorovinyl or 1 ,2- dichloro-2-fluoro-vinyl.
Haloalkynyl groups are alkynyl groups, respectively, which are substituted with one or more of the same or different halogen atoms and are, for example, 1-chloro-prop-2-ynyl.
Alkoxy means a radical -OR, where R is alkyl, e.g. as defined above. Alkoxy groups include, but are not limited to, methoxy, ethoxy, 1 -methylethoxy, propoxy, butoxy, 1 - methylpropoxy and 2-methylpropoxy.
Cyano means a -CN group.
Amino means an NH2 group.
Hydroxyl or hydroxy stands for a -OH group.
Aryl means a ring system which may be mono-, bi- or tricyclic. Examples of such rings include phenyl, naphthalenyl, anthracenyl, indenyl or phenanthrenyl. A preferred aryl group is phenyl.
Heteroaryl stands for aromatic ring systems comprising mono-, bi- or tricyclic systems wherein at least one oxygen, nitrogen or sulfur atom is present as a ring member. Monocyclic and bicyclic aromatic ring systems are preferred, monocyclic ring systems are more preferred. For example, monocyclic heteoraryl may be a 5- to 7-membered aromatic ring containing one to three heteroatoms selected from oxygen, nitrogen and sulfur, more preferably selected from nitrogen and sulfur. Bicyclic heteroaryl may be a 9- to 1 1-membered bicyclic ring containing one to five heteroatoms, preferably one to three heteroatoms, selected from oxygen, nitrogen and sulfur. Examples are furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl,
benzothiophenyl, benzofuranyl, benzimidazolyl, indazolyl, benzotriazolyl, benzothiazolyl, benzoxazolyl, imiazothiazoyl, quinolinyl, quinoxalinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl and naphthyridinyl, preferably pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furanyl, thienyl thiazolyl or thiadiazolyl. Heteroaryl rings do not contain adjacent oxygen ring atoms, adjacent sulfur ring atoms or adjacent oxygen and sulfur ring atoms. A link to a heteroaryl group can be via a carbon atom or via a nitrogen atom.
Carbocyclic ring system includes aryl and in addition their saturated or partially unsaturated analogues.
Heterocyclyl and heterocyclic ring system are used interchangeably and unless otherwise stated refer to include heteroaryl and in addition their saturated or partially unsaturated analogues. The different rings of bi- or tricyclic heterocyclic ring systems may be linked via one atom belonging to two different rings (spiro), via two adjacent ring atoms belonging to two different rings (annelated) or via two different, not adjacent ring atoms belonging to two different rings (bridged).
The presence of one or more possible asymmetric carbon atoms in a compound of formula I means that the compounds may occur in optically isomeric forms, i.e. enantiomeric or diastereomeric forms. Also atropisomers may occur as a result of restricted rotation about a single bond. Formula I is intended to include all those possible isomeric forms and mixtures thereof. The present invention includes all those possible isomeric forms and mixtures thereof for a compound of formula I. Likewise, formula I is intended to include all possible tautomers. The present invention includes all possible tautomeric forms for a compound of formula I.
In each case, the compounds of formula I according to the invention are in free form, in oxidized form as a N-oxide or in salt form, e.g. an agronomically usable salt form.
N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book "Heterocyclic N- oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
The following list provides definitions, including preferred definitions, for substituents G1, G2, T, Y1, Y2, n, p, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R 3, R14 and R15 with reference to compounds of formula I and other compounds of the invention carrying the same substituents. For any one of these substituents, any of the definitions given below may be combined with any definition of any other substituent given below or elsewhere in this document.
G1 and G2 are independently 0 or S.
G1 is preferably O.
G2 is preferably S.
T is CR11 or N, preferably CH or N, more preferably CH.
Y1 and Y2 are independently CR12 or N. Y1 is preferably CH or N, more preferably N.
Y2 is preferably CH or N; more preferably CH.
n is 1 or 2, preferably 2.
p is 1 or 2, providing that when n is 2, p is 1 , preferably p is 1.
Preferably, p is 1 and n is 2.
R1 and R2 each independently are Ci-C4alkyl, C3-C5cycloalkyl or Ci-C4haloalkyl.
Preferably R1 and R2 are each independently methyl or halomethyl, more preferably methyl, difluoromethyl or trifluoromethyl.
Preferably R1 is difluoromethyl or trifluoromethyl. Preferably R2 is methyl or difluoromethyl. In one group of compounds R1 is trifluoromethyl and R2 is methyl. In another group of compounds R1 and R2 are both difluoromethyl.
R3, R4, R5, R6, R7 and R8 each independently are hydrogen, halogen, cyano, C C4alkyl, C C4alkoxy, C3-C5cycloalkyl, C-|-C4haloalkyl or C-|-C4thioalkyl; more preferably hydrogen, halogen, methyl, thiomethyl or halomethyl, even more preferably hydrogen or methyl, most preferably hydrogen.
Alternatively, R3 is carboxyl, C C4alkoxycarbonyl, C1-C4haloalkoxycarbonyl, aminocarbonyl, (Cr^alkyljaminocarbonyl, (C1-C4haloalkyl)aminocarbonyl, (C
C4alkyl)2aminocarbonyl or (Ci-C haloalkyl)2aminocarbonyl, and preferably carboxyl or C C4alkoxycarbonyl and R4, R5, R6, R7 and R8 are hydrogen or R5 is carboxyl, C
C4alkoxycarbonyl, Ci-C4haloalkoxycarbonyl, aminocarbonyl, (Ci-C4alkyl)aminocarbonyl, (Ci- C4haloalkyl)aminocarbonyl, (CrC4alkyl)2aminocarbonyl or (Ci-C4haloalkyl)2aminocarbonyl and preferably carboxyl or Ci-C4alkoxycarbonyl, and R3, R5, R6, R7 and R8 are hydrogen.
Preferably R9 is a 9- to 1 1 -membered bicyclic, partially unsaturated carbocyclic or heterocyclic ring system, containing one ring member selected from the group consisting of C(=NOR13), C(=NR13), C(=NN(R13)2) or C(=NNR13S02R13), and optionally containing one or more ring member(s) selected from the group consisting of O, S, N, C(=0), (C=S), S(O), or S(0)2, said carbocyclic or heterocyclic ring system being further optionally substituted by one or more R14.
Preferably R9 is a 9- to 1 1 -membered partially unsaturated bicyclic carbocyclic ring system, containing one ring member selected from the group consisting of C(=NOR13), C(=NR13), C(=NN(R13)2) or C(=NNR13S02R13) and further optionally substituted by one R14.
Alternatively, R9 is a 9- to 11 -membered partially unsaturated bicyclic carbocyclic or heterocyclic ring system, containing one ring member being C(=NOR13), and optionally containing one or more ring member(s) selected from the group consisting of O, N or C(=0), said ring system being further optionally substituted by one or more R14.
Preferably, R10 is hydrogen, Ci-C alkyl, Ci-C4haloalkyl, C2-C6alkylcarbonyl, or C2- C6alkoxycarbonyl; more preferably hydrogen. Preferably, R11 is hydrogen, halogen or hydroxy; preferably hydrogen or hydroxy, more preferably hydrogen.
Preferably, R12 is hydrogen, halogen or cyano; preferably hydrogen or cyano, more preferably hydrogen.
Preferably, each R13 independently is hydrogen, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl,
C3-C6cycloalkyl, CrC6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, C2- C6alkylcarbonyl, C2-C6alkoxycarbonyl, C2-C6alkylaminocarbonyl, di-(C2- C6alkyl)aminocarbonyl; more preferably hydrogen, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C6cycloalkyl, Ci-C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl; even more preferably hydrogen, Ci-C4alkyl, C2-C4alkenyl, C2-C4alkynyl, C3-C6cycloalkyl, or d- C4haloalkyl; and most preferably hydrogen, Ci-C2alkyl, Ci-C2haloalkyl.
Preferably, each R14 independently is halogen, cyano, Ci-C6alkyl, C3-C7cycloalkyl, C C6alkoxy, C Csalkylthio or C-rC6alkylsulfonyl wherein alkyl, cycloalkyl and alkoxy are optionally substituted by halogen; preferably halogen, C -C4alkyl or C C4alkoxy wherein alkyl and alkoxy are optionally substituted by halogen; more preferably halogen, C-rC4alkyl or C-p C4alkoxy and most preferably fluoro, Ci-C4alkyl or C1-C4alkoxy.
Preferably, each R15 independently is fluoro, chloro, methyl or methoxy.
Preferably the compound of formula I is a compound wherein:
G1 is O
G2 is S;
T is CH or N;
Y1 and Y2 are independently CH or N;
n is 1 or 2;
p is 1 or 2, providing that when n is 2, p is 1 ;
R1 and R2 each independently are methyl or halomethyl;
R3, R4, R5, R6, R7 and R8 each independently are hydrogen, halogen, methyl, thiomethyl or halomethyl;
R9 is a 9- to 1 1-membered bicyclic partially unsaturated carbocyclic or heterocyclic ring system, containing one ring member selected from the group consisting of C(=NOR13),
C(=NR13), C(=NN(R13)2) or C(=NNR13S02R13), and optionally containing one or more ring member(s) selected from the group consisting of O, S, N, C(=0), (C=S), S(O), or S(0)2, said ring system being further optionally substituted by one or more R14;
R10 is hydrogen, Ci-C4alkyl, Ci-C haloalkyl, C2-C6alkylcarbonyl, or C2-C6alkoxycarbonyl, Each R13 independently from each other, is hydrogen, CrC6alkyl, Ci-C6haloalkyl,
each R14 independently from each other is halogen, Ci-C8alkyl, Ci-C8alkoxy,
or a salt or a N-oxide thereof. Preferably the compound of formula I is a compound wherein:
G is O
G2 is S;
T is CH or N;
Y1 and Y2 are independently CH or N;
n is 1 or 2;
p is 1 or 2, providing that when n is 2, p is 1 ;
R1 and R2 each independently are methyl or halomethyl;
R3, R4, R5, R6, R7 and R8 each independently are hydrogen, halogen, methyl, thiomethyl or halomethyl;
R9 is a 9- to 1 1-membered partially unsaturated bicyclic carbocyclic or heterocyclic ring system, containing one ring member being C(=NOR13), and optionally containing one or more ring member(s) selected from the group consisting of O, N or C(=0), said carbocyclic or heterocyclic ring system being further optionally substituted by one or more R14;
R10 is hydrogen,
Each R13 independently from each other, is hydrogen, C C6alkyl, Ci-C6haloalkyl, each R14 independently from each other is halogen, d-Cealkyl, C^Caalkoxy,
or a salt or a N-oxide thereof. Preferably the compound of formula I is a compound wherein G1, is O, G2 is S, G3 is O, Y1 is N, and Y2 is CH.
Preferably the compound of formula I is a compound wherein R1 and R2 each independently are methyl, difluoromethyl or trifluoromethyl and R3, R4, R5, R6, R7 and R8 each
independently are hydrogen, or methyl, and preferably hydrogen.
In another group of compounds of the invention G1 is O; G2 is S; T is CH or N; Y1 is N; Y2 is CH; n is 2; p is 1 ; R1 is difluoromethyl or trifluoromethyl; R2 is methyl or difluoromethyl; R3, R4, R5 R6, R7 and R8 are hydrogen; R9 is a 5- to 11 -membered mono-, bi- or tricyclic, saturated or partially unsaturated carbocyclic or heterocyclic ring system, containing one C(=NOR13) ring member and optionally containing at least one ring member selected from O, S, N, C(=0), (C=S), S(O), or S(0)2, said carbocyclic or heterocyclic ring system being further optionally substituted by one or two R14; R10 is hydrogen, Ci-C4alkyl, Ci-C4haloalkyl, C2- C6alkylcarbonyl, C2-C6alkoxycarbonyl; each R13 independently is hydrogen, Ci-C6alkyl, C2- C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, Ci-C3haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl; each R14 independently is halogen, Ci-C3alkyl, Ci-C6alkoxy, C
C6alkylthio, wherein alkyl and alkoxy are optionally substituted by halogen.
In another group of compounds of the invention G1 is O; G2 is S; T is CH or N; Y1 is N; Y2 is CH; n is 2; p is 1 ; R1 is difluoromethyl or trifluoromethyl; R2 is methyl or difluoromethyl; R3, R4, R5 R6, R7 and R8 are hydrogen; R9 is a 5- to 11 -membered mono-, bi- or tricyclic, saturated or partially unsaturated carbocyclic or heterocyclic ring system, containing one C(=NR13) ring member and optionally containing one or more ring member(s) selected from 0, S, N, C(=0), (C=S), S(O), or S(0)2, said carbocyclic or heterocyclic ring system being further optionally substituted by one or two R14; R10 is hydrogen, Ci-C4alkyl, Ci-C4haloalkyl, C2-C6alkylcarbonyl, C2-C3alkoxycarbonyl; each R13 independently is hydrogen, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, CrC6haloalkyl, C2-C6haloalkenyl, C2- C6haloalkynyl, C3-C6halocycloalkyl; each R14 independently is halogen, Ci-C6alkyl, d- Cealkoxy, Ci-Cealkylthio, wherein alkyl and alkoxy are optionally substituted by halogen.
In another group of compounds of the invention G1 is 0; G2 is S; T is CH or N; Y1 is N;
Y2 is CH; n is 2; p is 1 ; R1 is difluoromethyl or trifluoromethyl; R2 is methyl or difluoromethyl; R3, R4, R5 R6, R7 and R8 are hydrogen; R9 is a 5- to 11 -membered mono-, bi- or tricyclic, saturated or partially unsaturated carbocyclic or heterocyclic ring system, containing one C(=NN(R13)2) ring member and optionally containing one or more ring member(s) selected from O, S, N, C(=0), (C=S), S(O), or S(0)2, said carbocyclic or heterocyclic ring system being further optionally substituted by one or two R14; R10 is hydrogen, C1-C4alkyl, C
C4haloalkyl, C2-C6alkylcarbonyl, C2-C6alkoxycarbonyl; each R13 independently is hydrogen, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, CrC6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl; each R14 independently is halogen, d-C6alkyl, C C6alkoxy, Ci-C6alkylthio, wherein alkyl and alkoxy are optionally substituted by halogen.
In another group of compounds of the invention G1 is O; G2 is S; T is CH or N; Y1 is N; Y2 is CH; n is 2; p is 1 ; R1 is difluoromethyl or trifluoromethyl; R2 is methyl or difluoromethyl; R3, R4, R5 R6, R7 and R8 are hydrogen; R9 is a 5- to 11 -membered mono-, bi- or tricyclic, saturated or partially unsaturated carbocyclic or heterocyclic ring system, containing one C(=NNR13S02R13) ring member and optionally containing one or more ring member(s) selected from O, S, N, C(=0), (C=S), S(O), or S(0)2, said carbocyclic or heterocyclic ring system being further optionally substituted by one or two R14; R10 is hydrogen, Ci-C4alkyl, C C4haloalkyl, C2-C6alkylcarbonyl, C2-C6alkoxycarbonyl; each R13 independently is hydrogen, C Cealkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C-|-C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl; each R14 independently is halogen, C Cealkyl, C C6alkoxy, CrCsalkylthio, wherein alkyl and alkoxy are optionally substituted by halogen.
In another group of compounds of the invention G is O; G2 is S; T is CH; Y1 is N; Y2 is CH; n is 2; p is 1 ; R1 is difluoromethyl or trifluoromethyl; R2 is methyl or difluoromethyl; R3, R4, R5 R6, R7 and R8 are hydrogen; R9 is a 9- to 1 1 -membered bicyclic partially unsaturated carbocyclic or heterocyclic ring system, containing one C(=NOR13) ring member and optionally containing one or two ring members selected from O, S, N, C(=0), (C=S), S(O), or S(0)2, said carbocyclic or heterocyclic ring system being further optionally substituted by one or two R14; R10 is hydrogen; each R13 independently is hydrogen, CrCealkyl, C2- C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, Ci-Cshaloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl; each R14 independently is halogen, d-C4alkyl, CrC4alkoxy, Cr
C4alkylthio.
In another group of compounds of the invention G is O; G2 is S; T is CH; Y1 is N; Y2 is CH; n is 2; p is 1 ; R1 is difluoromethyl or trifluoromethyl; R2 is methyl or difluoromethyl; R3, R4, R5 R6, R7 and R8 are hydrogen; R9 is a 9- to 1 1 -membered bicyclic partially unsaturated carbocyclic or heterocyclic ring system, containing one C(=NR13) ring member and optionally containing one or two ring members selected from O, S, N, C(=0), (C=S), S(O), or S(0)2, said carbocyclic or heterocyclic ring system being further optionally substituted by one or two R14; R10 is hydrogen; each R13 independently is hydrogen, Ci-C6alkyl, C2-C6alkenyl, C2- C6alkynyl, C3-C6cycloalkyl, CrCshaloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3- C6halocycloalkyl; each R14 independently is halogen, C -C4alkyl, C1-C4alkoxy, C -C4alkylthio.
In another group of compounds of the invention G1 is O; G2 is S; T is CH; Y1 is N; Y2 is CH; n is 2; p is 1 ; R1 is difluoromethyl or trifluoromethyl; R2 is methyl or difluoromethyl; R3, R4, R5 R6, R7 and R8 are hydrogen; R9 is a 9- to 1 1 -membered bicyclic partially unsaturated carbocyclic or heterocyclic ring system, containing one C(=NN(R13)2 ring member and optionally containing one or two ring members selected from O, S, N, C(=0), (C=S), S(O), or S(0)2, said carbocyclic or heterocyclic ring system being further optionally substituted by one or two R14; R10 is hydrogen; each R13 independently is hydrogen, CrC6alkyl, C2- C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, Ci-C3haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl; each R14 independently is halogen, Ci-C4alkyl, Ci-C4alkoxy, Ci- C4alkylthio.
In another group of compounds of the invention G1 is O; G2 is S; T is CH; Y1 is N; Y2 is CH; n is 2; p is 1 ; R1 is difluoromethyl or trifluoromethyl; R2 is methyl or difluoromethyl; R3, R4, R5 R6, R7 and R8 are hydrogen; R9 is a 9- to 1 1 -membered bicyclic partially unsaturated carbocyclic or heterocyclic ring system, containing one C(=NNR13S02R13) ring member and optionally containing one or two ring members selected from O, S, N, C(=0), (C=S), S(O), or S(0)2, said carbocyclic or heterocyclic ring system being further optionally substituted by one or two R14; R10 is hydrogen; each R13 independently is hydrogen, C-|-C6alkyl, C2- C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, CrCshaloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl; each R14 independently is halogen, Ci-C4alkyl, C1-C4alkoxy, C
C4alkylthio.
For the avoidance of doubt, when n is 1 and p is 1 compounds of formula I have the formula according to formula l-a: N— O
(l-a)
in which R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, G1, G2, T, Y1 and Y2 have the definitions as described for formula I.
When n is 2 and p is 1 compounds of formula I have the formula according to formula l-b:
Figure imgf000011_0001
in which R1, R2 R3, R4, R5, R6, R7, R8, R9, R10, G1, G2, T, Y1 and Y2 have the definitions as described for formula I.
When n is 1 and p is 2, compounds of formula I have the formula according to formula l-c:
Figure imgf000011_0002
in which R1, R2 R3, R4, R5, R6, R7, R8, R9, R10, G1, G2, T, Y1 and Y2 have the definitions as described for formula I.
The invention also relates to compounds of formula l-a, formula l-b and formula l-c as shown above.
The invention also relates to compounds of formula l-d:
Figure imgf000011_0003
in which R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, G2, Y1 and Y2 have the definitions as described for formula I. Preferred definitions of R1, R2, R3, R4, R5, R6, R7, R8, R9, R 0, G2, Y1 and Y2 are as defined for formula I.
The invention also relates to compounds of formula l-e:
Figure imgf000012_0001
in which R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 have the definitions as described for formula I. Preferred definitions of R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are as defined for formula I.
The invention also relates to compounds of formula l-f:
Figure imgf000012_0002
wherein R3, R4, R5, R6, R7, R8, R9, R10, G1, G2, T, Y1, Y2, n and p have the definition as described for formula I. Preferred definitions of R3, R4, R5, R6, R7, R8, R9, R10, G1, G2, T, Y1, Y2, n and p are as defined for formula I.
The invention also relates to compounds of formula l-g:
Figure imgf000012_0003
in which R3, R4, R5, R6, R7, R8, R9, R10, G1, G2, T, Y1, Y2, n and p have the definitions as described for formula I. Preferred definitions of R3, R4, R5, R6, R7, R8, R9, R10, G1, G2, T, Y1, Y2, n and p are as defined for formula I.
The invention includes compounds of formula II:
Figure imgf000013_0001
wherein R3, R4, R5, R6, R7, R8, R9, R10, G2, T, Y1, Y2 , n and p are as defined for a compound of formula I and E is hydrogen or E1, wherein E1 is a protecting group, such as alkylcarbonyl, benzyl or alkoxycarbonyl, e.g. C C4 alkylcarbonyl, benzyl or C-rC4 alkoxycarbonyl, in particular acetyl, benzyl or tert-butoxycarbonyl. These compounds, including salts and N- oxides thereof, are useful as intermediates in the synthesis of compounds of formula I.
Preferred definitions of R3, R4, R5, R6, R7, R8, R9, R10, G2, T, Y1, Y2 , n and p are as defined for formula I.
Compounds of the present invention can be made as shown in the following schemes. Throughout this description, the group M, wherein R1, R2 and G1 are as defined for formula I, stands for:
Figure imgf000013_0002
(M)
The compounds of formula I, wherein R1 , R2, R3, R4, R5, R6, R7, R8, R9, R10, G1 , G2, T, Y1 , Y2, n and p are as defined for formula I can be obtained by transformation of a compound of formula IV, wherein the group M is defined above and R17 is hydroxy, halogen, preferably fluoro, chloro or bromo, or alkoxy, such as methoxy or ethoxy, with a compound of formula III, wherein R3, R4, R5, R6, R7, R8, R9, R10, G2, T, Y1 , Y2, n and p are as defined for formula I, and a base or an activating agent. This is shown in Scheme 1.
Scheme 1
Figure imgf000013_0003
The compounds of formula III, wherein R3, R4, R5, R6, R7, R8, R9, R10, G2, T, Y1, Y2, n and p are as defined for formula I can be obtained by transformation of a compound of formula V, wherein R3, R4, R5, R6, R7, R8, R9, R10, G2, T, Y1, Y2, n and p are as defined for formula I and E1 is a protecting group such as acetyl, benzyl or ieri-butoxycarbonyl, with a deprotecting agent such as a base, an acid or a hydrogenolysis catalytic system such as H2/Pd. This route is shown in Scheme 2.
Figure imgf000014_0001
The compounds of formula VI, wherein R3, R4, R5, R6, R7, R8, R9, R10, G2, T, Y1, Y2, n and p are as defined for formula I and E is hydrogen or E1, can be obtained by transformation of a compound of formula VII, wherein R3, R4, R5, R6, R7, R8, G2, T, Y1, Y2, n and p are as defined for formula I and E is hydrogen or E1, with a compound of formula VIII, wherein R9 and R10 are as defined for formula I, and hydroxylamine and sodium hypochlorite.
Alternatively, compounds of formula VI, wherein R3, R4, R5, R6, R7, R8, R9, R10, G2, T, Y1, Y2, n and p are as defined for formula I and E is hydrogen or E1, can be obtained stepwise by transformation of a compound of formula IX, wherein R3, R4, R5, R6, R7, R8, G2, T, Y1, Y2, n and p are as defined for formula I and E is hydrogen or E1, with a compound of formula VIII, wherein R9 and R10 are as defined for formula I, and an oxidant such as sodium hypochlorite, /V-chlorosuccinimide or diacetoxyiodobenzene. Compounds of formula IX, wherein R3, R4, R5, R6, R7, R8, G2, T, Y1, Y2, n and p are as defined for formula I and E is hydrogen or E1, can be obtained by transformation of a compound of formula VII, wherein R3, R4, R5, R6, R7, R8, G2, T, Y1, Y2, n and p are as defined for formula I and E is hydrogen or E1, with
hydroxylamine. These two routes are shown in Scheme 3.
Scheme 3
Figure imgf000014_0002
The compound of formula VIII, wherein R9 and R10 are as defined for formula I, can be obtained by transformation of a compound of formula X, wherein R9 is as defined for formula
I and R18 is In, MgCI, MgBr, Sn(R19)3, ZnCI, ZnBr or B(OR19)2, wherein either R19 is independently from each other hydrogen, C Ce alkyl or wherein two R19 together can form a C3-C8cycloalkyl, with a compound of formula XI, wherein R10 is as defined under formula I and Hal is a halogen, preferably chloro, bromo or iodo, and a catalyst, such as
tetrakistriphenylphosphinepalladium, palladium dichloride, [1 ,1-bis(diphenylphosphino) ferrocene]dichloropalladium(ll), palladium acetate or bis(diphenylphosphine)palladium(ll) chloride. This route is shown in Scheme 4.
Scheme 4
Figure imgf000015_0001
Alternatively, the compounds of formula VI, wherein R3, R4, R5, R6, R7, R8, R9, R10, T, n and p are as defined for formula I, G2 is S, Y1 is N, Y2 is CH, and E is hydrogen or E1, can be obtained by transformation of a compound of formula XII, wherein R3, R4, R5, R6, R7, R8, n and p are as defined for formula I and E is hydrogen or E1, with a compound of formula XIII, wherein R9 and R10 are as defined for formula I and Hal is a halogen, preferably chloro or bromo, and a base. This route is shown in Scheme 5.
Scheme 5
Figure imgf000015_0002
XII XIII
The compounds of formula XIII, wherein R9 and R10 are as defined for formula I and Hal is a halogen, preferably chloro or bromo, can be obtained by transformation of a compound of formula XIV, wherein each Hal independently from each other is a halogen, preferably chloro or bromo, with a compound of formula XIII, wherein R9 and R10 are as defined for formula I and Hal is a halogen, preferably chloro or bromo, and a base. This route is shown in Scheme 6.
Scheme 6
Figure imgf000015_0003
Surprisingly, it has now been found that the novel compounds of formula I have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.
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 novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and may be used for protecting numerous cultivated plants. The compounds of formula I can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later e.g. from phytopathogenic microorganisms.
It is also possible to use compounds of formula I as dressing agents for the treatment of plant propagation material, e.g., seed, such as fruits, tubers or grains, or plant cuttings (for example 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.
Furthermore the compounds according to present invention can be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage, in hygiene management.
In addition, the invention could be used to protect non-living materials from fungal attack, e.g. lumber, wall boards and paint.
The compounds of formula I are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Alternaria spp.), Basidiomycetes (e.g. Corticium spp., Ceratobasidium spp., Waitea spp., Thanatephorus spp., Rhizoctonia spp., Hemileia spp., Puccinia spp., Phakopsora spp., Ustilago spp., Tilletia spp.), Ascomycetes (e.g. Venturia spp., Blumeria spp., Erysiphe spp., Podosphaera spp., Uncinula spp., Monilinia spp., Sclerotinia spp., Colletotrichum spp., Glomerella spp., Fusarium spp.,
Gibberella spp., Monographella spp., Phaeosphaeria spp., Mycosphaerella spp., Cercospora spp., Pyrenophora spp., Rhynchosporium spp., Magnaporthe spp., Gaeumannomyces spp., Oculimacula spp., Ramularia spp., Botryotinia spp.) and Oomycetes (e.g. Phytophthora spp., Pythium spp., Plasmopara spp., Peronospora spp., Pseudoperonospora spp. Bremia spp). Outstanding activity is observed against downy mildew (e.g. Plasmopara viticola) and late blight (e.g. Phytophthora infestans). Furthermore, the novel compounds of formula I are effective against phytopathogenic gram negative and gram positive bacteria (e.g.
Xanthomonas spp, Pseudomonas spp, Erwinia amylovora, Ralstonia spp.) and viruses (e.g. tobacco mosaic virus).
Within the scope of present invention, target crops and/or 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 turf and ornamentals.
The useful plants and / or target crops in accordance with the invention include conventional as well as genetically enhanced or engineered varieties such as, for example, insect resistant (e.g. Bt. and VIP varieties) as well as disease resistant, herbicide tolerant (e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®) and nematode tolerant varieties. By way of example, suitable genetically enhanced or engineered crop varieties include the Stoneville 5599BR cotton and Stoneville 4892BR cotton varieties.
The term "useful plants" and/or "target crops" 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" and/or "target crops" 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.
The term "useful plants" and/or "target crops" 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 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-0 353 191. 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 plant as used herein is intended to embrace the place on which the plants are growing, where the plant propagation materials of the plants are sown or where the plant propagation materials of the plants will be placed 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. 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 may be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they may be conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
Suitable carriers and adjuvants, e.g. for agricultural use, can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890. The compounds of formula I are normally used in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g. fertilizers or micronutrient donors or other preparations, which influence the growth of plants. They can also be selective herbicides or non-selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
The compounds of formula I may be used in the form of (fungicidal) compositions for controlling or protecting against phytopathogenic microorganisms, comprising as active ingredient at least one compound of formula I or of at least one preferred individual compound as above-defined, in free form or in agrochemically usable salt form, and at least one of the above-mentioned adjuvants.
The invention provides a composition, preferably a fungicidal composition, comprising at least one compound formula I an agriculturally acceptable carrier and optionally an adjuvant. An agricultural acceptable carrier is for example a carrier that is suitable for agricultural use. Agricultural carriers are well known in the art. Preferably said composition may comprise at least one or more pesticidally active compounds, for example an additional fungicidal active ingredient in addition to the compound of formula I.
The compound of formula (I) may be the sole active ingredient of a composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate. An additional active ingredient may, in some cases, result in unexpected synergistic activities. Examples of suitable additional active ingredients include the following: Azoxystrobin (131860-33-8), Dimoxystrobin (149961-52-4), Enestrobin (238410-1 1-2), Fluoxastrobin (193740-76-0),
Kresoxim-methyl (143390-89-0), Metominostrobin (133408-50-1 ), Orysastrobin (248593-16- 0), Picoxystrobin (117428-22-5), Pyraclostrobin (175013-18-0), trifloxystrobin (141517-21-7), Azaconazole (60207-31-0), Bromuconazole (1 16255-48-2), Cyproconazole (94361-06-5), Difenoconazole (1 19446-68-3), Diniconazole (83657-24-3), Diniconazole-M (83657-18-5), Epoxiconazole (13385-98-8), Fenbuconazole (114369-43-6), Fluquinconazole (136426-54- 5), Flusilazole (85509-19-9), Flutriafol (76674-21 -0), Hexaconazole (79983-71 -4), Imazalil (58594-72-2), Imibenconazole (86598-92-7), Ipconazole (125225-28-7), Metconazole (1251 16-23-6), Myclobutanil (88671-89-0), Oxpoconazole (174212-12-5), Pefurazoate (5801 1 -68-0), Penconazole (66246-88-6), Prochloraz (67747-09-5), Propiconazole (60207- 90-1 ), Prothioconazole (178928-70-6), Simeconazole (149508-90-7), Tebuconazole
(107534-96-3), Tetraconazole (1 12281-77-3), Triadimefon (43121-43-3), Triadimenol (55219-65-3), Triflumizole (99387-89-0), Triticonazole (131983-72-7), Diclobutrazol (76738- 62-0), Etaconazole (60207-93-4), Fluconazole (86386-73-4), Fluconazole-cis (1 12839-32-4), Thiabendazole (148-79-8), Quinconazole (103970-75-8), Fenpiclonil (74738-17-3),
Fludioxonil (131341-86-1 ), Cyprodinil (121552-61 -2), Mepanipyrim (1 10235-47-7),
Pyrimethanil (531 12-28-0), Aldimorph (91315-15-0), Dodemorph (1593-77-7),
Fenpropimorph (67564-91-4), Tridemorph (81412-43-3), Fenpropidin (67306-00-7),
Spiroxamine (118134-30-8), Isopyrazam (881685-58-1 ), Sedaxane (874967-67-6), Bixafen (581809-46-3), Penthiopyrad (183675-82-3), Fluxapyroxad (907204-31 -3), Boscalid (188425- 85-6), Penflufen (494793-67-8), Fluopyram (658066-35-4), Mandipropamid (374726-62-2), Benthiavalicarb (413615-35-7), Dimethomorph (1 10488-70-5), Chlorothalonil (1897-45-6), Fluazinam (79622-59-6), Dithianon (3347-22-6), Metrafenone (220899-03-6), Tricyclazole (41814-78-2), Mefenoxam (70630-17-0), Metalaxyl (57837-19-1 ), Acibenzolar (126448-41 -7) (Acibenzolar-S-methyl (126448-41 -7)), Mancozeb (8018-01 -7), Ametoctradine (865318-97-4) Cyflufenamid (180409-60-3), and Kresoxim-methyl (143390-89-0), Ipconazole (125225-28- 7), Amisulbrom (348635-87-0), Cyflufenamid (180409-60-3), Ethaboxam (16650-77-3), Fluopicolide (2391 10-15-7), Fluthianil (304900-25-2), Isotianil (224049-04-1 ), Proquinazid (189278-12-4), Valiphenal (283159-90-0), 1-methyl-cyclopropene (3100-04-7), Trifloxystrobin (141517-21-7), Sulfur (7704-34-9), Copper ammoniumcarbonate (CAS 331 13-08-5); Copper oleate (CAS 1 120-44-1 ); Folpet (133-07-3), Quinoxyfen (124495-18-7), Captan (133-06-2), Fenhexamid (126833-17-8), Glufosinate and its salts (51276-47-2, 35597-44-5 (S-isomer)), Glyphosate (1071-83-6 ) and its salts (69254-40-6 (Diammonium), 34494-04-7
(Dimethylammonium), 38641-94-0 (Isopropylammonium), 40465-66-5 (Monoammonium), 70901-20-1 (Potassium), 70393-85-0 (Sesquisodium), 81591-81 -3 (Trimesium)), 1-methyl-3- difluoromethyl-1 H-pyrazole-4-carboxylic acid (2-dichloromethylene-3-ethyl-1-methyl-indan-4- yl)-amide (1072957-71 -1 ), 1-methyl-3-difluoromethyl-1 H-pyrazole-4-carboxylic acid (4'- methylsulfanyl-biphenyl-2-yl)-amide, 1-methyl-3-difluoromethyl-4H-pyrazole-4-carboxylic acid [2-(2,4-dichloro-phenyl)-2-methoxy-1-methyl-ethyl]-amide, (5-Chloro-2,4-dimethyl-pyridin-3- yl)-(2,3,4-trimethoxy-6-methyl-phenyl)-methanone, (5-Bromo-4-chloro-2-methoxy-pyridin-3- yl)-(2,3,4-trimethoxy-6-methyl-phenyl)-methanone, 2-{2-[(E)-3-(2,6-Dichloro-phenyl)-1- methyl-prop-2-en-(E)-ylideneaminooxymethyl]-phenyl}-2-[(Z)-methoxyimino]-N-methyl- acetamide, 3-[5-(4-Chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine.
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 mixture comprising at least one compound of formula I or at least one preferred individual compound as above-defined, in admixture with other fungicides, 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 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
phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, which comprises the application of a compound of formula I or of a preferred individual compound as above-defined as active ingredient to the plants, to parts of the plants or to the locus thereof, to the propagation material thereof, or to any part of the non-living materials.
Controlling or preventing means reducing infestation by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, to such a level that an improvement is demonstrated.
A preferred method of controlling or preventing an infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, 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. However, the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field. The compounds of formula I may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
A formulation, e.g. a composition containing the compound of formula I, and, if desired, a solid or liquid adjuvant or monomers for encapsulating the compound of formula I, may be prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface active
compounds (surfactants).
The agrochemical formulations and/or compositions 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 10g to 1 kg a.i./ha, most preferably from 20g to 600g a.i./ha. When used as seed drenching agent, convenient dosages are from 10mg to 1 g of active substance per kg of seeds.
Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations. The following non-limiting examples illustrate the above-described invention in more detail.
Example P1 :
Preparation of: 2-[3.5-bis(difluoromethyl')pyrazol-1-yll-1-r4-i4-[5-r(1 EV1-methoxyiminotetralin-
Figure imgf000022_0001
a) To a solution of 5-vinyltetralin-1-one (0.100 g, 0.581 mmol) in ethanol (1.16 mL, 0.581 mmol) was added O-methylhydroxylamine hydrochloride (0.0582 g, 0.697 mmol). The reaction mixture was stirred 1 h at rt. Water was then added followed by ethyl acetate and a saturated solution of sodium bicarbonate. The solution was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over Na2S04, filtered and concentrated to give /V-methoxy-5-vinyl-tetralin-1-imine as a light yellow oil. The product was used in the next step without further purification.
LCMS: 1.18min; [M+H]+ = 202 b) To th e com merci al ly avai l abl e fert-butyl 4-(4-formylthiazol-2-yl)piperidine-1 - carboxylate (0.300 g, 1 .01 mmol) in methanol (3.4 mL) was added hydroxylamine hydrochloride (0.106 g, 1.52 mmol) followed by sodium acetate (0.249 g, 3.04 mmol). The reaction mixture was stirred for 1 h30 at rt. All the volatiles were removed under vacuum, water was added and the residue was extracted with dichloromethane. The combined organic layers were washed with brine, dried over Na2S04, filtered and concentrated to give ferf-butyl 4-[4-[(E)-hydroxyiminomethyl]thiazol-2-yl]piperidine-1 - carboxylate as a white solid. The product was used in the next step without further purification.
LCMS: 0.89min; [M+H]+ = 312 To a solution of /V-methoxy-5-vinyl-tetralin-1-imine (0.107 g, 0.530 mmol) in methanol was added a drop of TFA followed by the lodobenzenediacetate (0.171 g, 0.530 mmol) and the ferf-butyl 4-[4-[(E)-hydroxyiminomethyl]thiazol-2-yl]piperidine-1 - carboxylate (0.150 g, 0.482 mmol). The reaction mixture was stirred for 1 h30 at rt.
The volatiles were removed under vacuum and the resulting oil was purified by Isco combiflash Rf using dichloromethane/ethyl acetate as eluent to give ierf-butyl 4-[4-[5- [(1 E)-1-methoxyiminotetralin-5-yl]-4,5-dihydroisoxazol-3-yl]thiazol-2-yl]piperidine-1- carboxylate as a white solid.
LCMS: 1.25min; [M+H]+ = 51 1
To a solution of ferf-butyl 4-[4-[5-[(1E)-1-methoxyiminotetralin-5-yl]-4,5- dihydroisoxazol-3-yl]thiazol-2-yl]piperidine-1 -carboxylate (0.120 g, 0.235 mmol) in dioxane (0.588 ml_, 0.235 mmol) was added a solution of HCI in dioxane (0.235 ml_, 0.940 mmol). The reaction mixture was stirred overnight at rt. The precipitate was filtered, purified, dissolve in dioxand and precipitated out using HCI in dioxane. The solid was filtered to give A/-methoxy-5-[3-[2-(4-piperidyl)thiazol-4-yl]-4,5- dihydroisoxazol-5-yl]tetralin-1-imine dihydrochloride as a yellow solid.
LCMS of the bis HCI salt: 0.81 min; method SQD; [M+H]+ = 41 1
To /V-methoxy-5-[3-[2-(4-piperidyl)thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]tetralin-1 - imine dihydrochloride (0.100 g, 0.207 mmol) in dichloromethane was added DIPEA (0.107 g, 0.143 ml_, 0.827 mmol) followed by HOAt (0.034 g, 0.25 mmol), EDCI HCI (0.048 g, 0.25 mmol) and 2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetic acid (0.047 g, 0.21 mmol). The reaction mixture was stirred overnight at rt. The reaction mixture was washed with HCI 1 M (x2) and the aqueous phase extracted with dichloromethane. The combined organic layers were washed with a saturated solution of sodium bicarbonate (x2), dried over Na2S04, filtered, concentrated and purified by Isco combiflash Rf using cyclohexane/ethyl acetate as eluent to give 2-[3,5- bis(difluoromethyl)pyrazol-1-yl]-1-[4-[4-[5-[(1 E)-1-methoxyiminotetralin-5-yl]-4,5- dihydroisoxazol-3-yl]thiazol-2-yl]-1-piperidyl]ethanone as a white solid.
LCMS: 1.14min; [M+H]+ = 619
1H NMR (400 MHz, CDCI3) δ ppm 1.67 - 1.88 (m, 4H), 2.06 - 2.22 (m, 2H), 2.55 - 2.78 (m, 4H), 2.79 - 2.90 (m, 1 H), 3.15 - 3.31 (m, 3H), 3.75 - 3.88 (m, 2H), 3.92 (s, 3H), 4.50 (br d, J=14.3 Hz, 1 H), 5.02 - 5.13 (m, 2H), 5.87 (dd, J=^ A, 8.1 Hz, 1 H), 6.59 (t, J=55.0 Hz, 1 H), 6.69 (s, 1 H), 6.81 (t, J=55.0 Hz, 1 H), 7.16 (t, J=7.9 Hz, 1 H), 7.41 (dd, J=7.7, 0.7 Hz, 1 H), 7.58 (s, 1 H), 7.92 (dd, J=7.9, 1.3 Hz, 1 H) Procedure 2:
Preparation of: N-KB-r5-r3-r2-ri-r2-r3.5-bis(difluorome^
piperidyllthiazol-4-yll-4,5-dihvdroisoxazol-5-ylltetralin-1-ylidenelaminolmethanesulfonamide
Figure imgf000024_0001
Triethylamine (9.72g) was added at 0-5°C to a solution of 2-(4-piperidyl)thiazole-4- carbaldehyde dihydrochloride (8.0) in dichloromethane (100ml_). Acetylchloride (2.80g) was added at 0-5°C, the reaction mixture was warmed up and stirred for 16h at 25°C. The reaction mixture was poured onto sodium bicarbonate solution (300ml_; 20% in water) and extracted with dichloromethane. The combined organic phases were washed with brine dried over magnesiumsulfate, filtered and concentrated. The residue was purified by
chromatographie over silica to give 2-(1 -acetyl-4-piperidyl)thiazole-4-carbaldehyde (3.05g) as yellow oil. . LCMS: 0.49min, [M+Hf = 239.
Figure imgf000024_0002
Hydroxylamine hydrochloride was added to a solution of 2-(1-acetyl-4-piperidyl)thiazole-4- carbaldehyde (3.9g) in ethanol (65ml_). After stirring for 16h at 25°C the reaction mixture was concentrated and water was added and the insoluble material was filtrated and dried to give 2-(1 -acetyl-4-piperidyl)thiazole-4-carbaldehyde oxime (2.53g) as white solid. LCMS: 0.54, MS: [M+H]+ = 254.
Figure imgf000025_0001
a) To a solution of 5-vinyltetralin-1-one (0.150 g, 0.871 mmol) in ethanol (2.90 mL, 0.871 mmol) was added methanesulfonohydrazide (0.125 g, 1.13 mmol). The reaction mixture was stirred overnight at 50°C. Water was then added followed by ethyl acetate and a saturated solution of sodium carbonate. The solution was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over Na2S04, f i l t e r e d a n d c o n c e n t r a t e d t o g i v e A/-[(E)-(5-vinyltetralin-1 - ylidene)amino]methanesulfonamide as white crystals.
The product was used in the next step without further purification.
LCMS: 0.92min; [M+H]+ = 265 ; [M-H]" = 263 b) To a solution of (4£)-2-(1-acetyl-4-piperidyl)thiazole-4-carbaldehyde oxime (0.150 g, 0.592 mmol) in DMF (1.48 mL, 0.592 mmol) was added hydrogen chloride (0.0259 g, 0.71 1 mmol) followed by oxone (0.207 g, 0.338 mmol). The reaction mixture was stirred for 3h at rt. LCMS showed completion. Water was added and the solution was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over MgS04, filtered, concentrated and purified by Isco combiflash Rf using dichloromethane/MeOH as eluent to give (4Z)-2-(1-acetyl-4-piperidyl)-/V-hydroxy- thiazole-4-carboximidoyl chloride as a yellow solid.
LCMS: 0.63-0.68min; [M+H]+ = 288 c) To a solution of A -[(E)-(5-vinyltetralin-1-ylidene)amino]methanesulfonamide (0.101 g, 0.382 mmol) and sodium acetate (0.035 g, 0.42 mmol) in acetonitrile (0.85 mL) was add ed d ropwi se a sol ution of (4Z)-2-(1-acetyl-4-piperidyl)-A/-hydroxy-thiazole-4- carboximidoyl chloride (0.100 g, 0.347 mmol) in acetonitrile (0.85 mL) at rt. The reaction mixture was stirred for 4h at 50°C. Water was added and the solution was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over MgSC , filtered, concentrated and purified by Isco combiflash Rf using DCM/MeOH as eluent to give /V-[(E)-[5-[3-[2-(1-acetyl-4-piperidyl)thiazol-4-yl]-4,5- dihydroisoxazol-5-yl]tetralin-1-ylidene]amino]methanesulfonamide as a white solid. LCMS: 0.81 min; [M+H]+ = 516 ; [M-H]" = 514 d) To a suspension of /V-[(E)-[5-[3-[2-(1-acetyl-4-piperidyl)thiazol-4-yl]-4,5- dihydroisoxazol-5-yl]tetralin-1-ylidene]amino]methanesulfonamide (0.125 g, 0.242 mmol) in ethanol (1.6 ml_) was added NaOH (0.645 g, 2.42 mmol). The reaction mixture was stirred for 2.5 h at 85°C. Water was added and the solution was adjusted to neutral pH with HCI 1 M. The aqueous phase was lyophilized and the resulting foam was washed with 9/1 DCM/MeOH. The filtrate was concentrated to give Λ/-[(Ε)-[5-[3- [2-(4-piperidyl)thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]tetralin-1- ylidene]amino]methanesulfonamide as a white solid (the product contained residual salts).
LCMS: 0.64min; [M+H]+ = 474 ; [M-H]" = 472 e) To a solution of A/-[(E)-[5-[3-[2-(4-piperidyl)thiazol-4-yl]-4,5-dihydroisoxazol-5- yl]tetralin-1-ylidene]amino]methanesulfonamide (0.100 g, 0.21 1 mmol) in dichloromethane (0.53 mL) was added DIPEA (0.109 g, 0.146 mL, 0.845 mmol) followed by HOAt (0.035 g, 0.25 mmol), EDCI HCI (0.049 g, 0.25 mmol) and 2-[3,5- bis(difluoromethyl)pyrazol-1-yl]acetic acid (0.057 g, 0.25 mmol). The reaction mixture was stirred overnight at rt. The reaction mixture was washed with HCI 1 M and the aqueous phase extracted with dichloromethane. The combined organic layers were washed with a sat solution of NaHC03, dried over Na2S04, filtered, concentrated and purified by Isco combiflash Rf using DCM/MeOH as eluent to give N-[(E)-[5-[3-[2-[1- [2-[3,5-bis(difluoromethyl)pyrazol-1 -yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5- dihydroisoxazol-5-yl]tetralin-1-ylidene]amino]methanesulfonamide as a yellow solid. LCMS: 0.96min; [M+H]+ = 682 ; [M-H]" = 680
1H NMR (400 MHz, CDCI3) δ ppm 1.73 - 1.93 (m, 2H), 1.94 - 2.07 (m, 2H), 2.13 - 2.30
(m, 2H), 2.46 - 2.61 (m, 2H), 2.67 - 2.96 (m, 3H), 3.19 (s, 3H), 3.23 - 3.37 (m, 3H), 3.83 - 3.95 (m, 2H), 4.56 (d, 13.6 Hz, 1 H), 5.08 - 5.21 (m, 2H), 5.93 (dd, 11 .0, 8.1 Hz, 1 H), 6.66 (t, 55.1 Hz, 1 H), 6.75 (s, 1 H), 6.87 (t, 55.1 Hz, 1 H), 7.26 (t, J=7.7 Hz, 1 H), 7.47 - 7.56 (m, 2H), 7.66 (s, 1 H), 8.12 (dd, J=7.7, 1.1 Hz, 1 H)
General procedure for the synthesis of vinyl intermediates used in the making of the oximes and hvdrazones. To a solution of arylchloride or arylbromide in dry DMF was added tributyl(vinyl)stannane (1.1 eq) followed by Pd(PPh3)4 (0.2 eq). The reaction mixture was stirred overnight at 1 10°C. Water was then added followed by ethyl acetate and the mixture was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over Na2S04, filtered, concentrated and purified by Isco combiflash Rf using cyclohexane/ethyl acetate as eluent to give the corresponding vinylated aryl.
Following the above mentioned reaction conditions 8-vinyltetralin-1-one was obtained from 8- chlorotetralin-1-one as a yellow oil in 94% yield.
LCMS: 0.96min ; no detected ionisation
Figure imgf000027_0001
Table 1 below illustrates examples of individual compounds of formula I according to the invention.
Table 1 : individual compounds of formula I according to the invention
Entry R1 R2 T Y1 Y2 G2 R13
No.
1 CF3 CF3 CH N CH 0 CH2CF3
2 CH3 CF3 CH N CH 0 CH2CF3
3 CHF2 CF3 CH N CH 0 CH2CF3
4 CF3 CH3 CH N CH 0 CH2CF3
5 CH3 CH3 CH N CH 0 CH2CF3
6 CHF2 CH3 CH N CH 0 CH2CF3
7 CF3 CHF2 CH N CH 0 CH2CF3
8 CH3 CHF2 CH N CH 0 CH2CF3
9 CHF2 CHF2 CH N CH 0 CH2CF3
10 CF3 CF3 N N CH 0 CH2CF3
11 CH3 CF3 N N CH 0 CH2CF3
12 CHF2 CF3 N N CH 0 CH2CF3
13 CF3 CH3 N N CH 0 CH2CF3
14 CH3 CH3 N N CH 0 CH2CF3
15 CHF2 CH3 N N CH 0 CH2CF3 CF3 CHF2 N N CH 0 CH2CF3
CH3 CHF2 N N CH 0 CH2CF3
CHF2 CHF2 N N CH 0 CH2CF3
CF3 CF3 CH N CH S CH2CF3
CH3 CF3 CH N CH S CH2CF3
CHF2 CF3 CH N CH S CH2CF3
CF3 CH3 CH N CH S CH2CF3
CH3 CH3 CH N CH S CH2CF3
CHF2 CH3 CH N CH S CH2CF3
CF3 CHF2 CH N CH S CH2CF3
CH3 CHF2 CH N CH S CH2CF3
CHF2 CHF2 CH N CH S CH2CF3
CF3 CF3 N N CH S CH2CF3
CH3 CF3 N N CH S CH2CF3
CHF2 CF3 N N CH S CH2CF3
CF3 CH3 N N CH S CH2CF3
CH3 CH3 N N CH S CH2CF3
CHF2 CH3 N N CH S CH2CF3
CF3 CHF2 N N CH S CH2CF3
CH3 CHF2 N N CH S CH2CF3
CHF2 CHF2 N N CH S CH2CF3
CF3 CF3 CH CH N S CH2CF3
CH3 CF3 CH CH N S CH2CF3
CHF2 CF3 CH CH N S CH2CF3
CF3 CH3 CH CH N s CH2CF3
CH3 CH3 CH CH N s CH2CF3
CHF2 CH3 CH CH N s CH2CF3
CF3 CHF2 CH CH N s CH2CF3
CH3 CHF2 CH CH N s CH2CF3
CHF2 CHF2 CH CH N s CH2CF3
CF3 CF3 N CH N s CH2CF3
CH3 CF3 N CH N s CH2CF3
CHF2 CF3 N CH N s CH2CF3
CF3 CH3 N CH N s CH2CF3
CH3 CH3 N CH N s CH2CF3 CHF2 CH3 N CH N S CH2CF3
CF3 CHF2 N CH N S CH2CF3
CH3 CHF2 N CH N S CH2CF3
CHF2 CHF2 N CH N S CH2CF3
CF3 CF3 CH N N S CH2CF3
CH3 CF3 CH N N S CH2CF3
CHF2 CF3 CH N N S CH2CF3
CF3 CH3 CH N N S CH2CF3
CH3 CH3 CH N N S CH2CF3
CHF2 CH3 CH N N S CH2CF3
CF3 CHF2 CH N N S CH2CF3
CH3 CHF2 CH N N S CH2CF3
CHF2 CHF2 CH N N S CH2CF3
CF3 CF3 N N N S CH2CF3
CH3 CF3 N N N S CH2CF3
CHF2 CF3 N N N S CH2CF3
CF3 CH3 N N N S CH2CF3
CH3 CH3 N N N S CH2CF3
CHF2 CH3 N N N S CH2CF3
CF3 CHF2 N N N S CH2CF3
CH3 CHF2 N N N s CH2CF3
CHF2 CHF2 N N N s CH2CF3
CF3 CF3 CH N CH 0 CH3
CH3 CF3 CH N CH 0 CH3
CHF2 CF3 CH N CH 0 CH3
CF3 CH3 CH N CH 0 CH3
CH3 CH3 CH N CH 0 CH3
CHF2 CH3 CH N CH 0 CH3
CF3 CHF2 CH N CH 0 CH3
CH3 CHF2 CH N CH 0 CH3
CHF2 CHF2 CH N CH 0 CH3
CF3 CF3 N N CH 0 CH3
CH3 CF3 N N CH 0 CH3
CHF2 CF3 N N CH 0 CH3
CF3 CH3 N N CH 0 CH3 86 CH3 CH3 N N CH 0 CH3
87 CHF2 CH3 N N CH 0 CH3
88 CF3 CHF2 N N CH 0 CH3
89 CH3 CHF2 N N CH 0 CH3
90 CHF2 CHF2 N N CH 0 CH3
91 CF3 CF3 CH N CH S CH3
92 CH3 CF3 CH N CH S CH3
93 CHF2 CF3 CH N CH S CH3
94 CF3 CH3 CH N CH S CH3
95 CH3 CH3 CH N CH S CH3
96 CHF2 CH3 CH N CH S CH3
97 CF3 CHF2 CH N CH S CH3
98 CH3 CHF2 CH N CH S CH3
99 CHF2 CHF2 CH N CH S CH3
100 CF3 CF3 N N CH S CH3
101 CH3 CF3 N N CH S CH3
102 CHF2 CF3 N N CH S CH3
103 CF3 CH3 N N CH S CH3
104 CH3 CH3 N N CH S CH3
105 CHF2 CH3 N N CH S CH3
106 CF3 CHF2 N N CH S CH3
107 CH3 CHF2 N N CH S CH3
108 CHF2 CHF2 N N CH S CH3
109 CF3 CF3 CH CH N S CH3
110 CH3 CF3 CH CH N s CH3
111 CHF2 CF3 CH CH N s CH3
112 CF3 CH3 CH CH N s CH3
113 CH3 CH3 CH CH N s CH3
114 CHF2 CH3 CH CH N s CH3
115 CF3 CHF2 CH CH N s CH3
116 CH3 CHF2 CH CH N s CH3
117 CHF2 CHF2 CH CH N s CH3
118 CF3 CF3 N CH N s CH3
119 CH3 CF3 N CH N s CH3
120 CHF2 CF3 N CH N s CH3 121 CF3 CH3 N CH N S CH3
122 CH3 CH3 N CH N S CH3
123 CHF2 CH3 N CH N S CH3
124 CF3 CHF2 N CH N S CH3
125 CH3 CHF2 N CH N S CH3
126 CHF2 CHF2 N CH N S CH3
127 CF3 CF3 CH N N S CH3
128 CH3 CF3 CH N N S CH3
129 CHF2 CF3 CH N N S CH3
130 CF3 CH3 CH N N S CH3
131 CH3 CH3 CH N N S CH3
132 CHF2 CH3 CH N N S CH3
133 CF3 CHF2 CH N N S CH3
134 CH3 CHF2 CH N N S CH3
135 CHF2 CHF2 CH N N S CH3
136 CF3 CF3 N N N S CH3
137 CH3 CF3 N N N S CH3
138 CHF2 CF3 N N N S CH3
139 CF3 CH3 N N N S CH3
140 CH3 CH3 N N N S CH3
141 CHF2 CH3 N N N s CH3
142 CF3 CHF2 N N N s CH3
143 CH3 CHF2 N N N s CH3
144 CHF2 CHF2 N N N s CH3
145 CF3 CF3 CH N CH 0 H
146 CH3 CF3 CH N CH 0 H
147 CHF2 CF3 CH N CH 0 H
148 CF3 CH3 CH N CH 0 H
149 CH3 CH3 CH N CH 0 H
150 CHF2 CH3 CH N CH 0 H
151 CF3 CHF2 CH N CH 0 H
152 CH3 CHF2 CH N CH 0 H
153 CHF2 CHF2 CH N CH 0 H
154 CF3 CF3 N N CH 0 H
155 CH3 CF3 N N CH 0 H 156 CHF2 CF3 N N CH 0 H
157 CF3 CH3 N N CH 0 H
158 CH3 CH3 N N CH 0 H
159 CHF2 CH3 N N CH 0 H
160 CF3 CHF2 N N CH 0 H
161 CH3 CHF2 N N CH 0 H
162 CHF2 CHF2 N N CH 0 H
163 CF3 CF3 CH N CH S H
164 CH3 CF3 CH N CH S H
165 CHF2 CF3 CH N CH S H
166 CF3 CH3 CH N CH S H
167 CH3 CH3 CH N CH S H
168 CHF2 CH3 CH N CH S H
169 CF3 CHF2 CH N CH S H
170 CH3 CHF2 CH N CH S H
171 CHF2 CHF2 CH N CH S H
172 CF3 CF3 N N CH S H
173 CH3 CF3 N N CH S H
174 CHF2 CF3 N N CH S H
175 CF3 CH3 N N CH S H
176 CH3 CH3 N N CH S H
177 CHF2 CH3 N N CH S H
178 CF3 CHF2 N N CH S H
179 CH3 CHF2 N N CH s H
180 CHF2 CHF2 N N CH s H
181 CF3 CF3 CH CH N s H
182 CH3 CF3 CH CH N s H
183 CHF2 CF3 CH CH N s H
184 CF3 CH3 CH CH N s H
185 CH3 CH3 CH CH N s H
186 CHF2 CH3 CH CH N s H
187 CF3 CHF2 CH CH N s H
188 CH3 CHF2 CH CH N s H
189 CHF2 CHF2 CH CH N s H
190 CF3 CF3 N CH N s H 191 CH3 CF3 N CH N S H
192 CHF2 CF3 N CH N S H
193 CF3 CH3 N CH N S H
194 CH3 CH3 N CH N S H
195 CHF2 CH3 N CH N S H
196 CF3 CHF2 N CH N S H
197 CH3 CHF2 N CH N S H
198 CHF2 CHF2 N CH N S H
199 CF3 CF3 CH N N S H
200 CH3 CF3 CH N N S H
201 CHF2 CF3 CH N N S H
202 CF3 CH3 CH N N S H
203 CH3 CH3 CH N N S H
204 CHF2 CH3 CH N N S H
205 CF3 CHF2 CH N N S H
206 CH3 CHF2 CH N N S H
207 CHF2 CHF2 CH N N S H
208 CF3 CF3 N N N S H
209 CH3 CF3 N N N S H
210 CHF2 CF3 N N N S H
211 CF3 CH3 N N N S H
212 CH3 CH3 N N N S H
213 CHF2 CH3 N N N S H
214 CF3 CHF2 N N N S H
215 CH3 CHF2 N N N S H
216 CHF2 CHF2 N N N s H where
a 216 compounds of formula (I. a):
Figure imgf000033_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. b 216 compounds of formula (I.b):
Figure imgf000034_0001
wherein R , R2 : R , G , T, Y and Y are as defined in Table 1 c) 216 compounds of formula I.c):
Figure imgf000034_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 d 216 compounds of formula (l.d):
Figure imgf000034_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 e 216 compounds of formula (I.e):
Figure imgf000034_0004
wherein R1, R2, R 3, G2, T, Y1 and Y2 are as defined in Table 1 f) 216 compounds of formula (l.f):
Figure imgf000035_0001
wherein R , R , R , G2, T, Y1 and Y2 are as defined in Table 1. g 216 compounds of formula (I. g):
Figure imgf000035_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. h 216 compounds of formula (I. h):
Figure imgf000035_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. i 216 compounds of formula (I. i):
Figure imgf000035_0004
wherein R1, R2, R 3, G2, T, Y and Y2 are as defined in Table 1. j 216 compounds of formula (l.j):
Figure imgf000035_0005
wherein R1, R2, R 3, G2, T, Y1 and Y2 are as defined in Table 1. k 216 compounds of formula (l.k):
Figure imgf000036_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1.
1) 216 com ounds of formula (I.I):
Figure imgf000036_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in m) 216 compounds of formula (l.m):
(l.m)
LR13
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. n 216 compounds of formula (l.n):
Figure imgf000036_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. o 216 compounds of formula (l.o):
Figure imgf000037_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 216 compounds of formula (l.p):
Figure imgf000037_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 q 216 compounds of formula (l.q):
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 r 216 compounds of formula (l.r):
Figure imgf000037_0004
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 s) 216 compounds of formula (l.s):
Figure imgf000038_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. t 216 compounds of formula (l.t):
Figure imgf000038_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. u) 216 compounds of formula (I. u):
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1.
Figure imgf000038_0003
v) 216 compounds of formula (l.v):
Figure imgf000038_0004
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 w) 216 compounds of formula (l.w):
Figure imgf000039_0001
wherein R1, R2, R13, G2, T, Y1 and Y are as defined in Table 1
Figure imgf000039_0002
y 216 compounds of formula (l.y):
Figure imgf000039_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 z) 216 compounds of formula (l.z):
Figure imgf000039_0004
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 aa) 216 compounds of formula (l.aa):
Figure imgf000040_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. ab 216 compounds of formula (l.ab):
Figure imgf000040_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. ac 216 compounds of formula (l.ac):
Figure imgf000040_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. ad 216 compounds of formula (I. ad):
Figure imgf000040_0004
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. ae) 216 compounds of formula (l.ae):
Figure imgf000041_0001
ag) 216 compounds of formula (Lag):
Figure imgf000041_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 ah 216 compounds of formula (I. ah):
Figure imgf000041_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 ai) 216 compounds of formula (l.ai):
Figure imgf000042_0001
aj ) 2 6 compounds of formula (I.aj):
Figure imgf000042_0002
wherein R \ R , R , G^, T, Y and Y2 are as defined in Table 1 . ak) 216 compounds of formula (l.ak):
Figure imgf000042_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 . al) 216 compounds of formula (I.al):
Figure imgf000042_0004
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 am) 216 compounds of formula I. am):
Figure imgf000043_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 an) 216 compounds of formula (I.an :
Figure imgf000043_0002
wherein R1, R2, R 3, G2, T, Y and Y2 are as defined in Table 1 ao 216 compounds of formula (l.ao):
Figure imgf000043_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 ap 216 compounds of formula (Lap):
Figure imgf000043_0004
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 aq 216 compounds of formula (l.aq):
Figure imgf000044_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. ar) 216 compounds of formula (l.ar):
Figure imgf000044_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. as 216 compounds of formula (I. as):
Figure imgf000044_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. at) 216 compounds of formula (I. at):
Figure imgf000045_0001
au) 216 compounds of formula (l.au):
Figure imgf000045_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. av) 216 compounds of formula (l.av):
Figure imgf000045_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 aw) 216 compounds of formula (Law):
Figure imgf000046_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. ax) 216 compounds of formula (I. ax):
Figure imgf000046_0002
ay) 216 compounds of formula (Lay):
Figure imgf000046_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. az) 216 compounds of formula (l.az):
Figure imgf000046_0004
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 ba) 216 compounds of formula l.ba):
Figure imgf000047_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 bb) 216 compounds of formula (l.bb):
wherein R1, R2, R 3, G2, T, Y and Y2 are as defined in Table 1.
Figure imgf000047_0002
be) 216 compounds of formula (I. be):
Figure imgf000047_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1.
bd) 216 compounds of formula (l.bd):
Figure imgf000048_0001
wherein R1, R2, R13, G2, T, Y1 and Y^ are as defined in Table 1. be 216 compounds of formula (I. be):
Figure imgf000048_0002
wherein R1, R2, R13, G2, T, Y1 and are as defined in Table 1. bf) 216 compounds of formula (l.bf):
Figure imgf000048_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. bg) 216 compounds of formula (l.bg):
Figure imgf000048_0004
wherein R1, R2, R 3, G2, T, Y and Y are as defined in Table 1. bh) 216 compounds of formula (l.bh):
Figure imgf000049_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. bi) 216 compounds of formula (l.bi):
Figure imgf000049_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 bj ) 216 compounds of formula (l.bj):
Figure imgf000049_0003
wherein R1, R2, R 3, G2, T, Y and Y2 are as defined in Table 1. bk) 216 compounds of formula (l.bk):
Figure imgf000050_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. bl) 216 compounds of formula (l.bl):
Figure imgf000050_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 bm 216 compounds of formula (l.bm):
Figure imgf000050_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. bn) 216 compounds of formula (l.bn):
Figure imgf000050_0004
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. bo) 216 compounds of formula (I. bo):
Figure imgf000051_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. bp) 216 compounds of formula (I. bp):
Figure imgf000051_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. bq) 216 compounds of formula (l.bq):
Figure imgf000051_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. br)216 compounds of formula (l.br):
Figure imgf000052_0001
wherein R , R , R , G , T, Y and Y are as defined in Table 1. bs) 216 compounds of formula (l.bs):
Figure imgf000052_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 bt 216 compounds of formula (l.bt):
Figure imgf000052_0003
wherein R1, R2, R3, G2, T, Y and Y2 are as defined in Table 1. bu) 216 compounds of formula (l.bu):
Figure imgf000052_0004
wherein R1, R2, R 3, G2, T, Y and Y2 are as defined in Table 1 . bv) 216 compounds of formula (l.bv):
Figure imgf000053_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. bw) 216 compounds of formula (l.bw):
Figure imgf000053_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. bx) 216 compounds of formula (l.bx):
Figure imgf000053_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. by) 216 compounds of formula (I. by):
Figure imgf000054_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. bz 216 compounds of formula (l.bz):
Figure imgf000054_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. ca 216 compounds of formula (l.ca):
Figure imgf000054_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. cb) 216 compounds of formula (l.cb):
Figure imgf000054_0004
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. cc) 216 compounds of formula (l.cc):
Figure imgf000055_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. cd) 216 compounds of formula l.cd):
Figure imgf000055_0002
wherein R1, R2, R 3, G2, T, Y1 and Y2 are as defined in Table 1. ce) 216 compounds of formula (l.ce):
Figure imgf000055_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. cf) 216 compounds of formula (l.cf):
Figure imgf000056_0001
eg) 216 compounds of formula (I. eg):
Figure imgf000056_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 eh) 216 compounds of formula (l.ch):
Figure imgf000056_0003
wherein R1, R2, R13, G2, T, Y and Y2 are as defined in Table 1 ci) 216 compounds of formula (l.ci):
Figure imgf000056_0004
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. cj) 216 compounds of formula (l.cj):
Figure imgf000057_0001
wherein R , FT, R13, G , T, Y and Y are as defined in Table 1 . ck) 216 compounds of formula (l .ck):
Figure imgf000057_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 . cl) 216 compounds of formula (l.cl):
Figure imgf000057_0003
wherein R1, R2, R 3, G2, T, Y1 and Y2 are as defined in Table 1 . cm) 216 compounds of formula (I . cm):
Figure imgf000057_0004
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 . cn) 216 compounds of formula (l.cn):
Figure imgf000058_0001
wherein R1, R2, R13, G2, T, Y and Y2 are as defined in Table 1. co) 216 compounds of formula (l.co):
Figure imgf000058_0002
cp) 216 compounds of formula (l.cp):
Figure imgf000058_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. cq) 216 compounds of formula (l.cq):
Figure imgf000059_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. cr) 216 compounds of formula (l.cr):
Figure imgf000059_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. cs) 216 compounds of formula (l.cs):
Figure imgf000059_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. ct) 216 compounds of formula (l.ct):
Figure imgf000059_0004
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. cu) 216 compounds of formula (l.cu):
Figure imgf000060_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. cv) 216 compounds of formula (l.cv):
Figure imgf000060_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. cw) 216 compounds of formula (Lew :
Figure imgf000060_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. cx) 216 compounds of formula (l.cx):
Figure imgf000060_0004
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 . cy) 216 compounds of formula (Ley):
Figure imgf000061_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. cz) 216 compounds of formula (l.cz):
Figure imgf000061_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. da 216 compounds of formula (I. da):
Figure imgf000061_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. db) 216 compounds of formula (l.db):
Figure imgf000062_0001
dc) 216 compounds of formula (l.dc): 3
Figure imgf000062_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. dd) 216 compounds of formula (l.dd):
Figure imgf000062_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. de) 216 compounds of formula (l.de):
Figure imgf000062_0004
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. df) 216 compounds of formula (l.df):
Figure imgf000063_0001
wherein R1, R2, R13, G2, T, Y1 and ΎΔ are as defined in Table 1. dg) 216 compounds of formula (l.dg):
Figure imgf000063_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. dh 216 compounds of formula (l.dh):
Figure imgf000063_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. di) 216 compounds of formula (l.di):
Figure imgf000063_0004
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. dj) 216 compounds of formula (l.dj):
Figure imgf000064_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. dk) 216 compounds of formula (l.dk):
Figure imgf000064_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. dl 216 compounds of formula (l.dl):
Figure imgf000064_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. dm) 216 compounds of formula (I. dm):
Figure imgf000064_0004
wherein R1, R2, R 3, G2, T, Y and Y2 are as defined in Table 1. dn) 216 compounds of formula (l.dn):
Figure imgf000065_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. do) 216 compounds of formula (I.do):
Figure imgf000065_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. dp) 216 compounds of formula (I. dp):
Figure imgf000065_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. dq) 216 compounds of formula (l.dq):
Figure imgf000065_0004
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. dr) 216 compounds of formula (l.dr):
Figure imgf000066_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. ds) 216 compounds of formula (l.ds):
Figure imgf000066_0002
wherein R1, R2, R 3, G2, T, Y and Y2 are as defined in Table 1. dt 216 compounds of formula (l.dt):
Figure imgf000066_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. du) 216 compounds of formula (l.du):
Figure imgf000066_0004
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. dv) 216 compounds of formula (l.dv):
Figure imgf000067_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. dw) 216 compounds of formula (l.dw):
Figure imgf000067_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. dx) 216 compounds of formula (l.dx):
Figure imgf000067_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. dy) 216 compounds of formula (l.dy):
Figure imgf000068_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. dz) 216 compounds of formula (l.dz):
Figure imgf000068_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. eb) 216 compounds of formula (l.eb):
Figure imgf000068_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1 ec) 216 compounds of formula (l.ec):
Figure imgf000069_0001
wherein R1, R2, R 3, G2, T, Y and Y2 are as defined in Table 1. ed 216 compounds of formula (Led):
Figure imgf000069_0002
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. ee) 216 compounds of formula (l.ee):
Figure imgf000069_0003
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. ef 216 compounds of formula (l.ef):
Figure imgf000069_0004
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. eg) 216 compounds of formula (Leg):
Figure imgf000070_0001
wherein R1, R2, R13, G2, T, Y1 and Y2 are as defined in Table 1. eh 216 compounds of formula (I. eh):
Figure imgf000070_0002
Throughout this description, temperatures are given in degrees Celsius and "m.p." means melting point. LC/MS means Liquid Chromatography Mass Spectroscopy and the description of the apparatus and the method is:
Spectra were recorded on a Mass Spectrometer from Waters (SQD or ZQ Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range: 30-60 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 350°C, Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650 L/Hr, Mass range: 100 to 900 Da) and an 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: Waters UPLC HSS T3 , 1.8 Dm, 30 x 2.1 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: gradient: gradient: 0 min 0% B, 100%A; 1.2-1.5min 100% B; Flow (ml/min) 0.85
Table 2: LC/MS data of synthesized molecules
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
74
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
The compounds according to the present invention can be prepared according to the 5 above-mentioned reaction schemes, in which, unless otherwise stated, the definition of each variable is as defined above for a compound of formula (I).
Biological examples
In the following examples compounds listed are those from table 2.
10 Phvtoohthora infestans I tomato / leaf disc preventative (tomato late blight1)
Tomato leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf disks are incubated at 16°C and 75% rh under a light regime of 24 h darkness followed by 12 h light /
15 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application).
Compounds (from table 2) 1 , 2 , 3 , 4 , 6 , 7 , 8 , 9 , 10 , 1 1 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 20 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 and 47 at 200 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.
25 Phvtoohthora infestans I potato / preventative (potato late blight") 2-week old potato plants cv. Bintje are sprayed in a spray chamber with the formulated test compound diluted in water. The test plants are inoculated by spraying them with a sporangia suspension 2 days after application. The inoculated test plants are incubated at 18° C with 14 h light/day and 100 % rh in a growth chamber and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (5 - 7 days after application).
Compounds (from table 2) 1 , 6 , 7 , 12 and 22 at 200 ppm give at least 80% disease control in this test when compared to untreated control plants under the same conditions, which show extensive disease development.
Phytophthora infestans I potato / curative (potato late blight)
2-week old potato plants cv. Bintje are inoculated by spraying them with a sporangia suspension one day before application. The inoculated plants are sprayed in a spray chamber with the formulated test compound diluted in water. The inoculated test plants are incubated at 18° C with 14 h light/day and 100 % rh in a growth chamber and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (3 - 4 days after application). Compounds (from table 2) 1 , 7 , 12 and 22 at 200 ppm give at least 80% disease control in this test when compared to untreated control plants under the same conditions, which show extensive disease development.
Phytophthora infestans I potato / long lasting (potato late blight1)
2-week old potato plants cv. Bintje are sprayed in a spray chamber with the formulated test compound diluted in water. The test plants are inoculated by spraying them with a sporangia suspension 6 days after application. The inoculated test plants are incubated at 18° C with 14 h light/day and 100 % rh in a growth chamber and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (9 - 1 1 days after application).
Compounds (from table 2) 1 , 6 , 7 , 12 and 22 at 200 ppm give at least 80% disease control in this test when compared to untreated control plants under the same conditions, which show extensive disease development.
Plasmopara viticola I grape / leaf disc preventative (grape downy mildew)
Grape vine leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf disks are incubated at 19°C and 80% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (6 - 8 days after application).
Compounds (from table 2) 1 , 8 , 12 , 15 , 16 , 17 , 18 , 19 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 36 , 37 , 38 , 39 , 40 , 41 and 42 at 200 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.
Plasmopara viticola I grape / preventative (grape downy mildew)
5-week old grape seedlings cv. Gutedel are sprayed in a spray chamber with the formulated test compound diluted in water. The test plants plants are inoculated by spraying a sporangia suspension on their lower leaf surface one day after application. The inoculated test plants are incubated at 22° C and 100% rh in a greenhouse and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (6 - 8 days after application). Compounds (from table 2) 1 , 6 , 7 , 12 and 22 at 200 ppm give at least 80% disease control in this test when compared to untreated control plants under the same conditions, which show extensive disease development.
Plasmopara viticola I grape / curative (grape downy mildew)
5-week-old grape seedlings cv. Gutedel are inoculated by spraying a sporangia suspension on their lower leaf surface one day before application. The inoculated grape plants are sprayed in a spray chamber with the formulated test compound diluted in water. The inoculated test plants are incubated at 22° C and 100% rh in a greenhouse and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (4 - 6 days after application).
Compounds (from table 2) 12 and 22 at 200 ppm give at least 80% disease control in this test when compared to untreated control plants under the same conditions, which show extensive disease development.
Plasmopara viticola I grape / long lasting (grape downy mildew)
5-week old grape seedlings cv. Gutedel are sprayed in a spray chamber with the formulated test compound diluted in water. The test plants are inoculated by spraying a sporangia suspension on their lower leaf surface 6 days after application. The inoculated test plants are incubated at 22° C and 100% rh in a greenhouse and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (1 1 - 13 days after application).
Compounds (from table 2) 1 , 6 , 7 , 12 and 22 at 200 ppm give at least 80% disease control in this test when compared to untreated control plants under the same conditions, which show extensive disease development. Pythium ultimum I liquid culture (seedling damping off)
Mycelia fragments and oospores 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 test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal mycelia/spore mixture is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 2-3 days after application.
Compounds (from table 2) 22 , 28 , 30 , 33 , 39 and 40 at 20 ppm give at least 80% disease control in this test when compared to untreated control under the same conditions, which show extensive disease development.

Claims

What is claimed is:
Figure imgf000082_0001
wherein,
G1 and G2 are independently O or S;
T is CR11 or N;
Y1 and Y2 are independently CR12 or N;
n is 1 or 2;
p is 1 or 2, providing that when n is 2, p is 1 ;
R1 and R2 each independently are CrC4alkyl, C3-C5cycloalkyl or CrC4haloalkyl;
R3, R4, R5, R6, R7 and R8 each independently are hydrogen, halogen, cyano, C -C4alkyl, CV
C4alkoxy, C3-C5cycloalkyl, C -C4haloalkyl, or C -C4thioalkyl;
R9 is a 5- to 1 1-membered mono-, bi- or tricyclic, saturated or partially unsaturated carbocyclic or heterocyclic ring system, containing at least one ring member selected from the group consisting of C(=NOR13), C(=NR13), C(=NN(R13)2) or C(=NNR13S02R13), and optionally containing one or more ring member(s) selected from the group consisting of 0, S,
N, C(=0), (C=S), S(O), or S(0)2, said carbocyclic or heterocyclic ring system being further optionally substituted by one or more R14;
R10 is hydrogen, Ci-C alkyl, Ci-C4haloalkyl, C2-C6alkylcarbonyl, C2-C6alkoxycarbonyl, C2-
Cealkylaminocarbonyl, di-(C2-C6alkyl)aminocarbonyl or a 5- to 10-membered mono- or bicyclic, saturated, partially unsaturated or aromatic carbocyclic or heterocyclic ring system optionally containing 1 to 4 ring members selected from the group consisting of nitrogen, oxygen and sulfur;
R11 is hydrogen, halogen or hydroxyl;
R12 is hydrogen, halogen or cyano;
each R13 independently is hydrogen, Ci-C6alkyl, C2-C6alkenyl, C2-C5alkynyl, C3- C6cycloalkyl, C C5haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, C2- C6alkylcarbonyl, C2-C6alkoxycarbonyl, C2-C6alkylaminocarbonyl, or di-(C2- C6alkyl)aminocarbonyl or is a 5- to 10-membered aromatic, saturated or partially saturated monocyclic or fused bicyclic ring system optionally containing 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, where the ring system is directly attached to the rest of the molecule or via a C -C4alkyl, C2-C4alkenyl, C2-C4alkynyl, d. C4alkoxy or C _C4alklythio group, and wherein the ring system is optionally substituted by one or more R15 and does not contain more than two oxygen atoms and not more than two sulfur atoms;
each R14 independently is halogen, cyano, amino, nitro, hydroxyl, mercapto, Ci-C8alkyl, C2- C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl-Ci-C4alkyl, C3-C8cycloalkyl-Ci- C4alkoxy, C3-C8cycloalkyl-Ci-C4alkylthio, Ci-C8alkoxy, C3-C8cycloalkoxy, Ci-C8alkenyloxy, C2-C8alkynyloxy, CrC8alkylthio, CrC8alkylsulfonyl, CrCsalkylsulfinyl, C3-C8cycloalkylthio, C3- Cscycloalkylsulfonyl, C3-C8cycloalkylsulfinyl, aryl, aryloxy, arylthio, arylsulfonyl, arylsulfinyl, aryl-Ci-C4alkyl, aryl-Ci-C4alkoxy, aryl-Ci-C4alkylthio, heterocyclyl, heterocycyl-Ci-C alkyl, heterocycyl-Ci-C4alkoxy, heterocycyl-CrC4alkylthio, NH(Ci-C8alkyl), N(Ci-C8alkyl)2, C C alkylcarbonyl, C3-C8cycloalkylcarbonyl, C2-C8alkenylcarbonyl, C2-C8alkynylcarbonyl, wherein alkyl, alkenyl, alkynyl, cycloalkyi, alkoxy, alkenyloxy, alkynyloxy and cycloalkoxy are optionally substituted by halogen, and wherein aryl and heterocyclyl are optionally substituted by one or more R15;
each R15 independently is halogen, cyano, C1-C4alkyl, CrC4haloalkyl, C-|-C4alkoxy or C-r C4haloalkoxy,
or a salt or a N-oxide thereof.
2. A compound according to claim 1 , wherein R10 is hydrogen.
3. A compound according to claim 1 , wherein R9 is a 9- to 1 1-membered bicyclic, partially unsaturated carbocyclic or heterocyclic ring system, containing one ring member selected from the group consisting of C(=NOR13), C(=NR13), C(=NN(R13)2) or C(=NNR13S02R13), and optionally containing at least one ring member selected from the group consisting of O, S, N, C(=0), (C=S), S(O), or S(0)2, said carbocyclic or heterocyclic ring system being further optionally substituted by one or more R14.
4. A compound according to claim 1 , wherein
G is O
G2 is S;
T is CH or N;
Y1 and Y2 are independently CH or N;
n is 1 or 2;
p is 1 or 2, providing that when n is 2, p is 1 ;
R1 and R2 each independently are methyl or halomethyl;
R3, R4, R5, R6, R7 and R8 each independently are hydrogen, halogen, methyl, thiomethyl or halomethyl; R9 is a 9- to 1 1 -membered bicyclic partially unsaturated carbocyclic or heterocyclic ring system, containing one ring member selected from the group consisting of C(=NOR13), C(=NR13), C(=NN(R13)2) or C(=NNR13S02R13), and optionally containing one or more ring member(s) selected from the group consisting of 0, S, N, C(=0), (C=S), S(O), or S(0)2, said ring system being further optionally substituted by one or more R14;
R10 is hydrogen, d-dalkyl, Ci-C4haloalkyl, C2-C6alkylcarbonyl, or C2-C6alkoxycarbonyl, Each R13 independently from each other, is hydrogen, d-dalkyl, d-dhaloalkyl, each R14 independently from each other is halogen, d-Csalkyl, d-dalkoxy,
or a salt or a N-oxide thereof.
5. A compound according to claim 1 , wherein
G1 is O
G2 is S;
T is CH or N;
Y1 and Y2 are independently CH or N;
n is 1 or 2;
p is 1 or 2, providing that when n is 2, p is 1 ;
R1 and R2 each independently are methyl or halomethyl;
R3, R4, R5, R6, R7 and R8 each independently are hydrogen, halogen, methyl, thiomethyl or halomethyl;
R9 is a 9- to 1 1 -membered partially unsaturated bicyclic carbocyclic or heterocyclic ring system, containing one ring member being C(=NOR13), and optionally containing one or more ring member(s) selected from the group consisting of O, N or C(=0), said carbocyclic heterocyclic ring system being further optionally substituted by one or more R14;
R10 is hydrogen,
Each R13 independently from each other, is hydrogen, CrC6alkyl, CrC6haloalkyl, each R14 independently from each other is halogen, d-Cealkyl, d-dalkoxy,
or a salt or a N-oxide thereof.
6. The compound according to any one of claims 1 to 5, wherein G1, is O, G2 is S, G3 is O, Y1 is N, and Y2 is CH.
7. The compound according to any one of claims 1 to 6, wherein p is 1 and n is 2. 8. The compound according to any one of the claims 1 to 7, wherein R1 and R2 each independently are methyl, difluoromethyl or trifluoromethyl and R3, R4, R5, R6, R7 and R8 each independently are hydrogen, or methyl, and preferably hydrogen.
5 9. A compound according to anyone of claims 1 to 3, wherein R3 is carboxyl, Ci-
C4alkoxycarbonyl, CrC4haloalkoxycarbonyl, aminocarbonyl, (Ci-C4alkyl)aminocarbonyl, (Ci- C4haloalkyl)aminocarbonyl, (Ci-C4alkyl)2aminocarbonyl or (Ci-C4haloalkyl)2aminocarbonyl, and preferably carboxyl or CrC4alkoxycarbonyl and R4, R5, R6, R7 and R8 are hydrogen or R5 is carboxyl, CrC4alkoxycarbonyl, Ci-C4haloalkoxycarbonyl, aminocarbonyl, (Ci- 10 C4alkyl)aminocarbonyl, (Ci-C4haloalkyl)aminocarbonyl, (C-i-C4alkyl)2aminocarbonyl or (d- C4haloalkyl)2aminocarbonyl and preferably carboxyl or Ci-C4alkoxycarbonyl, and R3, R5, R6, R7 and R8 are hydrogen.
A compound of formula II
Figure imgf000085_0001
wherein R3, R4, R5, R6, R7, R8, R9, R10, G2, T, Y1, Y2 , n and p are as defined in anyone of Claims 1-9 for a compound of formula I, and E is hydrogen or E1, wherein E1 is a protecting group, and salts and N-oxides thereof.
20 11. A composition comprising at least one compound as defined in any one of claims 1 to 10 and an agriculturally acceptable carrier, optionally comprising an adjuvant, and optionally comprising one or more additional pesticidally active compounds.
12. A method of controlling or preventing an infestation of plants, propagation material 25 thereof, harvested crops or of non-living materials by phytopathogenic or spoilage
microorganisms or organisms potentially harmful to man, which comprises the application of a compound as defined in any one of claims 1 to 1 1 , to the plant, to parts of the plants or to the locus thereof, to propagation material thereof or to any part of the non-living materials.
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US9266876B2 (en) 2012-02-02 2016-02-23 Actelion Pharmaceuticals Ltd. 4-(benzoimidazol-2-yl)-thiazole compounds and related aza derivatives
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US10047080B2 (en) 2015-01-15 2018-08-14 Idorsia Pharmaceuticals Ltd. (R)-2-methyl-piperazine derivatives as CXCR3 receptor modulators
US10053457B2 (en) 2015-01-15 2018-08-21 Idorsia Pharmaceuticals Ltd. Hydroxyalkyl-piperazine derivatives as CXCR3 receptor modulators
JPWO2017047337A1 (en) * 2015-09-18 2018-03-22 株式会社エス・ディー・エス バイオテック Process for producing 4- (4-formylthiazolyl) piperidine compound
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US11274076B2 (en) 2016-02-08 2022-03-15 Gowan Company, L.L.C. Process for preparing 1, 2-benzenedimethanol compound
US11903387B2 (en) 2016-02-08 2024-02-20 Gowan Company, L.L.C. Fungicidal composition
WO2019048988A1 (en) 2017-09-08 2019-03-14 Pi Industries Ltd. Novel fungidal heterocyclic compounds
WO2019048989A1 (en) 2017-09-08 2019-03-14 Pi Industries Ltd. Novel fungicidal heterocyclic compounds
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