WO2015007453A1 - Dérivés hétérobicycliques microbiocides - Google Patents

Dérivés hétérobicycliques microbiocides Download PDF

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WO2015007453A1
WO2015007453A1 PCT/EP2014/062884 EP2014062884W WO2015007453A1 WO 2015007453 A1 WO2015007453 A1 WO 2015007453A1 EP 2014062884 W EP2014062884 W EP 2014062884W WO 2015007453 A1 WO2015007453 A1 WO 2015007453A1
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alkyl
crc
nhch
cycloalkyl
alkynyl
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PCT/EP2014/062884
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Fredrik Cederbaum
Clemens Lamberth
Thomas James HOFFMAN
Werner Zambach
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Syngenta Participations Ag
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems

Definitions

  • the present invention relates to microbiocidal heterobicyclic derivatives, e.g. as active ingredients, which have microbiocidal activity, in particular fungicidal activity.
  • the invention also relates to preparation of these heterobicyclic derivatives, to heterobicyclic derivatives used as intermediates in the preparation of these heterobicyclic derivatives, to preparation of these intermediates, to agrochemical compositions which comprise at least one of the heterobicyclic derivatives, to preparation of these compositions and to use of the
  • heterobicyclic 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:
  • X 1 , X 2 and X 3 are independently O, S or NR 5 ;
  • R 1 is hydrogen, C C 6 alkyl, C 2 -C 6 alkynyl or C 3 -C 6 cycloalkyl in which the alkyl, alkynyl and cycloalkyi groups are optionally substituted by one or more R 6 ;
  • R 4 is C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, aryl or heterocyclyl, in which the alkynyl, cycloalkyi, aryl and heterocyclyl groups are optionally substituted by one or more R 6 ;
  • R 5 is hydrogen, C C 6 alkyl, C C 6 alkoxy, C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyl, C 2 - C 6 alkynyloxy, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyloxy or aryl, in which the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyi and aryl groups are optionally substituted by one or more R 6 ;
  • R 6 is hydrogen, halogen, cyano, hydroxyl, amino, CrC 6 alkyl, CrC 6 haloalkyl, CrC 6 alkoxy, CrC 6 haloalkoxy, d-C 6 alkylthio, Ci-Cehaloalkylthio, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 - C 6 alkenyloxy, C 2 -C 6 alkenylthio, C 2 -C6haloalkenyloxy, C 2 -C 6 haloalkenylthio, C 2 -C 6 alkynyl, C 2 - C 6 alkynyloxy, C 2 -C 6 alkynylthio, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 3 -C 6 cycloalkyloxy, C 3 - Cecycloalkylthio, C 3 -
  • L 1 and L 2 are independently a direct bond, -C(R 6 ) 2 -z, -C(R 6 ) 2 -C(R 6 ) 2 -z, -C(R 6 ) 2 -C(R 6 ) 2 -C(R 6 ) 2 - z, -NR 5 -z, -NR 5 -C(R 6 ) 2 -z, -C(R 6 ) 2 -NR 5 -z, -NR 5 -C(R 6 ) 2 -C(R 6 ) 2 -z, -C(R 6 ) 2 -NR 5 -C(R 6 ) 2 -z, -C(R 6 ) 2 -NR 5 -C(R 6 ) 2 -z, -C(R 6 ) 2 -NR 5 -C(R 6 ) 2 -z, -C(R 6 ) 2 -NR 5 -C(R 6 ) 2 -z, -C
  • 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 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, 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 or iso-amyl.
  • 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 C 2 -C 3 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 CCI 3 CCI 2 .
  • 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.
  • Monocyclic and bicyclic aromatic ring systems are preferred.
  • monocyclic heteocyclyl may be a 4- to 7-membered ring containing one to three heteroatoms selected from oxygen, nitrogen and sulfur, more preferably selected from nitrogen and oxygen.
  • Bicyclic heterocyclyl may be a 7- to 1 1 -membered bicyclic ring containing one to five heteroatoms, preferably one to three heteroatoms, selected from oxygen, nitrogen and sulfur.
  • the different rings of bi- and tricyclic heterocyclyl 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).
  • saturated heterocyclyl examples include azetidinyl, oxetanyl, thietanyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydrothienyl, pyrazolidinyl, imidazolidinyl, oxazolidinyl, thiazolidinyl, isoxazolidinyl, isothiazolidinyl, oxadiazolidinyl, thiadiazolidinyl, dioxolanyl, dithiolanyl, piperidinyl, piperazinyl, tetrahydropyranyl, tetrahydrothiopyranyl, dithianyl and morpholinyl.
  • Examples for partially unsaturated heterocyclyl are pyrrolinyl, dihydrofuranyl, dihydrothienyl, pyrazolinyl, imidazolinyl, oxazolinyl, thiazolinyl, isoxazolinyl, isothiazinyl, oxadiazolinyl, thiadiazolinyl, dihydropyranyl, dihydrothiopyranyl, oxathiolyl and oxazinyl.
  • aromatic heterocyclyl examples include furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, benzothiophenyl, benzofuranyl,
  • Heterocyclyl rings do not contain adjacent oxygen ring atoms, adjacent sulfur ring atoms or adjacent oxygen and sulfur ring atoms.
  • a link to a heterocyclyl group can be via a carbon atom or via a nitrogen atom.
  • 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 .
  • X 1 , X 2 and X 3 are independently O or S or NR 5 , preferably O or S.
  • X 1 is preferably S.
  • X 2 is preferably O.
  • X 3 is preferably O.
  • R 1 is hydrogen, CrC 6 alkyl, C 2 -C 6 alkynyl or C3-C 6 cycloalkyl in which the alkyl, alkynyl and cycloalkyl groups are optionally substituted by one or more R 6 .
  • R 1 is hydrogen, Ci-C 6 alkyl or C 3 -C 6 cycloalkyl in which the alkyl and cycloalkyl groups are optionally substituted by one or more R 6 , more preferably hydrogen or CrC 6 alkyl, even more preferably hydrogen or methyl.
  • R 4 is C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, aryl or heterocyclyl, in which the alkynyl, cycloalkyl, aryl and heterocyclyl groups are optionally substituted by one or more R 6 .
  • R 4 is C 3 -C 6 cycloalkyl, aryl or heterocyclyl, in which cycloalkyl, aryl and heterocyclyl are optionally substituted by one or more R 6 , more preferably aryl or 5- to 6- membered aromatic heterocyclic ring system, even more preferably phenyl or thienyl.
  • R 5 is hydrogen, CrC 6 alkyl, C C 6 alkoxy, C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyl, C 2 -C 6 alkynyloxy, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyloxy or aryl, in which the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and aryl groups are optionally substituted by one or more R 6 ;
  • R 5 is hydrogen, CrC 6 alkyl, Ci-C6alkoxy; more preferably hydrogen or d- C 6 alkyl, even more preferably hydrogen or methyl.
  • R 6 is hydrogen, halogen, cyano, nitro, hydroxyl, amino, CrC 6 alkyl, CrC 6 haloalkyl, Cr C 6 alkoxy, CrC 6 haloalkoxy, CrC 6 alkylthio, CrC 6 haloalkylthio, C 2 -C 6 alkenyl, C 2 - C 6 haloalkenyl, C 2 -C 6 alkenyloxy, C 2 -C 6 alkenylthio, C 2 -C 6 haloalkenyloxy, C 2 -C 6 haloalkenylthio, C 2 -C 6 alkynyl, C 2 -C 6 alkynyloxy, C 2 -C 6 alkynylthio, C 3 -C 6 cycloalkyl, C 3 -C 6 alocycloalkyl, C 3 -C 6 alocycloalkyloxy, C 3 -C 6 cycloalkylthio,
  • R 6 is halogen, cyano, nitro, hydroxyl, amino, CrC 6 alkyl, Ci-Cehaloalkyl, d-
  • L and L 2 are independently a direct bond, -C(R 6 ) 2 -z, -C(R 6 ) 2 -C(R 6 ) 2 -z, -C(R 6 ) 2 -C(R 6 ) 2 - C(R 6 ) 2 -z, -NR 5 -z, -NR 5 -C(R 6 ) 2 -z, -C(R 6 ) 2 -NR 5 -z, -N R 5 -C(R 6 ) 2 -C(R 6 ) 2 -z, -C(R 6 ) 2 -NR 5 -C(R 6 ) 2 -z, - C(R 6 ) 2 -C(R 6 ) 2 -NR 5 -z, -C(R 6 ) 2 -0-z, -C(R 6 ) 2 -0-C(R 6 ) 2 -z, -C(R 6 ) 2 -C(R 6 ) 2
  • L 1 is preferably -C(R 6 ) 2 -z, -C(R 6 ) 2 -C(R 6 ) 2 -z, -C(R 6 ) 2 -NR 5 -z or -C(R 6 ) 2 -0-z, more preferably -C(R 6 ) 2 -z or -C(R 6 ) 2 -C(R 6 ) 2 -z, even more preferably -C(CH 3 ) 2 -z.
  • L 2 is preferably -C(R 6 ) 2 -z, -C(R 6 ) 2 -C(R 6 ) 2 -z, -C(R 6 ) 2 -C(R 6 ) 2 -C(R 6 ) 2 -z, -C(R 6 ) 2 -NR 5 -z or
  • the compound of formula I is a compound wherein:
  • X 1 , X 2 and X 3 are independently O, S or NR 5 ;
  • R is hydrogen, CrC 6 alkyl or C 3 -C 6 cycloalkyl in which the alkyl and cycloalkyi groups are optionally substituted by one or more R 6 ;
  • R 4 is C 3 -C 6 cycloalkyl, aryl or heterocyclyl, in which cycloalkyi, aryl and heterocyclyl are optionally substituted by one or more R 6 ;
  • R 5 is hydrogen, CrC 6 alkyl or Ci-C 6 alkoxy
  • R 6 is halogen, cyano, nitro, hydroxyl, amino, CrC 6 alkyl, d-Cehaloalkyl, CrC 6 alkoxy, C C 6 haloalkoxy, CrC 6 alkylthio, CrC 6 haloalkylthio, C2-C 6 alkenyl, C2-C 6 haloalkenyl, C 2 - C 6 alkenyloxy, C 2 -C 6 haloalkenyloxy, C2-C 6 alkynyl, C2-C 6 alkynyloxy, C 3 -C 6 cycloalkyl, C 3 - C 6 halocycloalkyl, C 3 -C 6 cycloalkyloxy or C 3 -C 6 halocycloalkyloxy;
  • L 1 is -C(R 6 ) 2 -z, -C(R 6 ) 2 -C(R 6 ) 2 -z, -C(R 6 ) 2 -NR 5 -z or -C(R 6 ) 2 -0-z;
  • L 2 is -C(R 6 ) 2 -z, -C(R 6 ) 2 -C(R 6 ) 2 -z, -C(R 6 ) 2 -C(R 6 ) 2 -C(R 6 ) 2 -z, -C(R 6 ) 2 -NR 5 -z or -C(R 6 ) 2 -0-z; or a salt or a N-oxide thereof.
  • the compound of formula I is a compound wherein:
  • X 1 , X 2 and X 3 are independently O, S or NR 5 ;
  • R 1 is hydrogen, Ci-C 6 alkyl or C 3 -C 6 cycloalkyl in which the alkyl and cycloalkyi groups are optionally substituted by one or more R 6 ;
  • R 4 is aryl or 5- to 6-membered aromatic heterocyclic ring system
  • R 5 is hydrogen or CrC 6 alkyl
  • R 6 is halogen, cyano, CrC 6 alkyl, C C 6 haloalkyl, CrC 6 alkoxy, CrC 6 haloalkoxy, C 2 -C 6 alkenyl,
  • L 1 is -C(R 6 ) 2 -z or -C(R 6 ) 2 -C(R 6 ) 2 -z;
  • L 2 is -C(R 6 ) 2 -C(R 6 ) 2 -z or -C(R 6 ) 2 -0-z;
  • the compound of formula I is a compound wherein:
  • X 1 , X 2 and X 3 are independently O, S or NR 5 ;
  • R 1 is hydrogen or Ci-C 6 alkyl
  • R 4 is aryl or 5- to 6-membered aromatic heterocyclic ring system
  • R 5 is hydrogen or Ci-C 6 alkyl
  • R 6 is halogen, cyano, CrC 6 alkyl, CrC 6 haloalkyl, CrC 6 alkoxy, CrC 6 haloalkoxy, C 2 -C 6 alkynyl or C 3 -C 6 cycloalkyl;
  • L 1 is -C(R 6 ) 2 -z or -C(R 6 ) 2 -C(R 6 ) 2 -z;
  • L 2 is -C(R 6 ) 2 -C(R 6 ) 2 -z or -C(R 6 ) 2 -0-z;
  • the compound of formula I is a compound wherein:
  • X 1 , X 2 and X 3 are independently O, S or NR 5 ;
  • R 1 is hydrogen or Ci-C 6 alkyl
  • R 4 is phenyl or thienyl
  • R 5 is hydrogen or methyl
  • R 6 is fluoro, chloro, cyano, methyl, trifluoromethyl, methoxy, ethynyl or cyclopropyl.
  • L 1 is -C(R 6 ) 2 -z or -C(R 6 ) 2 -C(R 6 ) 2 -z;
  • L 2 is -C(R 6 ) 2 -C(R 6 ) 2 -z or -C(R 6 ) 2 -0-z;
  • the compound of formula I is a compound wherein: X 1 , X 2 and X 3 are independently 0, S or NR 5 ;
  • R 1 is hydrogen or methyl
  • R 4 is phenyl or thienyl
  • R 5 is hydrogen or methyl
  • L 1 is -C(CH 3 ) 2 -z;
  • L 2 is CH 2 CH(0(CrC 6 alkyl))-z;
  • the compound of formula I is a compound wherein:
  • X 1 , X 2 and X 3 are independently O or S;
  • R 1 is hydrogen, d-C 6 alkyl or C 3 -C 6 cycloalkyl in which the alkyl and cycloalkyi groups are optionally substituted by one or more R 6 ;
  • R 4 is C 3 -C 6 cycloalkyl, aryl or heterocyclyl, in which cycloalkyi, aryl and heterocyclyl are optionally substituted by one or more R 6 ;
  • R 6 is halogen, cyano, nitro, hydroxyl, amino, C C 6 alkyl, CrC 6 haloalkyl, C C 6 alkoxy, C C 6 haloalkoxy, C C 6 alkylthio, C C 6 haloalkylthio, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 - C 6 alkenyloxy, C 2 -C 6 haloalkenyloxy, C 2 -C 6 alkynyl, C 2 -C 6 alkynyloxy, C 3 -C 6 cycloalkyl, C 3 - C 6 halocycloalkyl, C 3 -C 6 cycloalkyloxy or C 3 -C 6 halocycloalkyloxy;
  • L 1 is -C(R 6 ) 2 -z, -C(R 6 ) 2 -C(R 6 ) 2 -z, -C(R 6 ) 2 -NR 5 -z or -C(R 6 ) 2 -0-z;
  • L 2 is -C(R 6 ) 2 -z, -C(R 6 ) 2 -C(R 6 ) 2 -z, -C(R 6 ) 2 -C(R 6 ) 2 -C(R 6 ) 2 -z, -C(R 6 ) 2 -NR 5 -z or -C(R 6 ) 2 -0-z;
  • the compound of formula I is a compound wherein:
  • X 1 , X 2 and X 3 are independently O or S;
  • R 1 is hydrogen, CrC 6 alkyl or C 3 -C 6 cycloalkyl in which the alkyl and cycloalkyi groups are optionally substituted by one or more R 6 ;
  • R 4 is aryl or 5- to 6-membered aromatic heterocyclic ring system
  • R 6 is halogen, cyano, CrC 6 alkyl, CrC 6 haloalkyl, CrC 6 alkoxy, CrC 6 haloalkoxy, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 2 -C 6 alkynyloxy, C 3 -C 6 cycloalkyl;
  • L 1 is -C(R 6 ) 2 -z or -C(R 6 ) 2 -C(R 6 ) 2 -z;
  • L 2 is -C(R 6 ) 2 -C(R 6 ) 2 -z or -C(R 6 ) 2 -0-z;
  • the compound of formula I is a compound wherein:
  • X 1 , X 2 and X 3 are independently O or S;
  • R 1 is hydrogen or C C 6 alkyl;
  • R 4 is aryl or 5- to 6-membered aromatic heterocyclic ring system
  • R 6 is halogen, cyano, C C 6 alkyl, C C 6 haloalkyl, C C 6 alkoxy, CrC 6 haloalkoxy, C 2 -C 6 alkynyl or C 3 -C 6 cycloalkyl;
  • L 1 is -C(R 6 ) 2 -z or -C(R 6 ) 2 -C(R 6 ) 2 -z;
  • L 2 is -C(R 6 ) 2 -C(R 6 ) 2 -z or -C(R 6 ) 2 -0-z;
  • the compound of formula I is a compound wherein:
  • X 1 , X 2 and X 3 are independently O or S;
  • R 1 is hydrogen or CrC 6 alkyl
  • R 4 is phenyl or thienyl
  • R 6 is fluoro, chloro, cyano, methyl, trifluoromethyl, methoxy, ethynyl or cyclopropyl.
  • L 1 is -C(R 6 ) 2 -z or -C(R 6 ) 2 -C(R 6 ) 2 -z;
  • L 2 is -C(R 6 ) 2 -C(R 6 ) 2 -z or -C(R 6 ) 2 -0-z;
  • the compound of formula I is a compound wherein:
  • X 1 , X 2 and X 3 are independently O or S;
  • R 1 is hydrogen or methyl
  • R 4 is phenyl or thienyl
  • L 1 is -C(CH 3 ) 2 -z;
  • L 2 is CH 2 CH(0(CrC 6 alkyl))-z;
  • the compound of formula I is a compound wherein X 1 is S, X 2 is O and X 3 is O.
  • n also relates to compounds of formula l-a:
  • X 1 , X 2 , X 3 , R 2 , R 3 , R 4 , L 1 and L 2 have the definitions as described for formula I.
  • Preferred definitions of X 1 , X 2 , X 3 , R 2 , R 3 , R 4 , L 1 and L 2 are as defined for formula I.
  • the invention also relates to compounds of formula l-b:
  • X 1 , X 2 , X 3 , R 1 , R 3 , R 4 , L 1 and L 2 have the definition as described for formula I.
  • Preferred definitions of X 1 , X 2 , X 3 , R 1 , R 3 , R 4 , L 1 and L 2 are as defined for formula I .
  • the invention also relates to compounds of formula l-c:
  • X 1 , X 2 , X 3 , R 1 , R 2 , R 3 , R 4 and L 2 have the definitions as described for formula I.
  • Preferred definitions of X 1 , X 2 , X 3 , R 1 , R 2 , R 3 , R 4 and L 2 are as defined for formula I .
  • the invention also relates to compounds of formula l-d:
  • X 1 , X 2 , X 3 , R 1 , R 2 , R 3 , L 1 and L 2 have the definitions as described for formula I.
  • Preferred definitions of X 1 , X 2 , X 3 , R 1 , R 2 , R 3 , L 1 and L 2 are as defined for formula I .
  • the invention also relates to compounds of formula l-e:
  • X 1 , X 2 , X 3 , R 1 , R 2 , R 3 , R 4 and L 1 have the definitions as described for formula I.
  • Preferred definitions of X 1 , X 2 , X 3 , R 1 , R 2 , R 3 , R 4 and L 1 are as defined for formula I .
  • the invention also relates to compounds of formula l-f:
  • X 1 , X 2 , X 3 , R 1 , R 2 , R 3 , L 1 and L 2 have the definitions as described for formula I.
  • the compounds of formula I wherein X 1 , X 2 , X 3 , R 1 , R 2 , R 3 , R 4 , L 1 and L 2 are as defined for formula I can be obtained by transformation of a compound of formula II, wherein X 1 , X 2 , X 3 , R 1 , R 2 , R 3 and L 1 are as defined for formula I with a compound of formula III, wherein R 4 and L 2 are as defined for formula I and R 7 is halogen, preferably chloro or bromo, or a sulfonate, preferably a mesylate or tosylate, with a base. This is shown in Scheme 1.
  • the compounds of formula II wherein X 1 , X 2 , X 3 , R 1 , R 2 , R 3 and L 1 are as defined for formula I can be obtained by transformation of a compound of formula IV, wherein X 1 , X 2 , X 3 R 1 , R 2 , R 3 and L 1 are as defined for formula I and R 8 is CrC 6 alkyl, with a base, suchg as sodium hydride or potassium tert-butoxide. This is shown in Scheme 2.
  • the compounds of formula IV wherein X 1 , X 2 , X 3 , R 1 , R 2 , R 3 and L 1 are as defined for formula I and R 8 is d-C 6 alkyl can be obtained by transformation of a compound of formula V, wherein X 1 , X 2 , R 1 and R 2 are as defined for formula I and R 8 is CrC 6 alkyl, with a compound of formula VI, wherein R 3 and L 1 are as defined for formula I, and a phosgene derivative, such as bis(trichloromethyl)carbonate (BTC) and a base.
  • BTC bis(trichloromethyl)carbonate
  • the compounds of formula IV wherein X 1 , X 2 , X 3 , R 1 , R 2 , R 3 and L 1 are as defined for formula I and R 8 is CrC 6 alkyl
  • a compound of formula V wherein X 1 , X 2 , R 1 and R 2 are as defined for formula I and R 8 is CrC 6 alkyl
  • a compound of formula VII wherein R 3 and L 1 are as defined for formula I and Hal is halogen, preferably fluoro or chloro, and a base.
  • the compounds of formula II wherein X 1 , X 2 , X 3 , R 1 , R 2 , R 3 and L are as defined for formula I can be obtained by transformation of a compound of formula VIII, wherein X 1 , X 2 , R 1 , R 2 , R 3 and L 1 are as defined for formula I with a compound of formula (IX), such as phosgene or a phosgene derivative, and a base. This is shown in Scheme 5.
  • a compound of formula (IX) such as phosgene or a phosgene derivative
  • the compounds of formula VIII, wherein X 1 , X 2 , R 1 , R 2 , R 3 and L 1 are as defined for formula I can be obtained by transformation of a compound of formula X, wherein X 1 , X 2 , R 1 and R 2 are as defined for formula I and R 9 is hydroxy, halogen or CrC 6 alkoxy, with a compound of formula (VI), wherein R 3 and L 1 are as defined for formula I, and a base. This is shown in Scheme 6.
  • 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.
  • fungicide as used herein means a compound that controls, modifies, or prevents the growth of fungi.
  • fungicidally effective amount means the quantity of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Controlling or modifying effects include all deviation from natural development, such as killing, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection.
  • 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 Fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses.
  • These Fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses are for example:
  • Absidia corymbifera Alternaria spp, Aphanomyces spp, Ascochyta spp, Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terrus, Aureobasidium spp.
  • Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. contributing B. cinerea, Candida spp. including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis spp, Cercospora spp. including C.
  • Coccidioides immitis Coccidioides immitis, Cochliobolus spp, Colletotrichum spp. including C. musae,
  • Cryptococcus neoformans Diaporthe spp, Didymella spp, Drechslera spp, Elsinoe spp, Epidermophyton spp, Erwinia amylovora, Erysiphe spp. including E. cichoracearum,
  • Eutypa lata Fusarium spp. including F. culmorum, F. graminearum, F. langsethiae, F.
  • Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp, Peronosclerospora spp. Including P. maydis, P. philippinensis and P. sorghi, Peronospora spp, Phaeosphaeria nodorum, Phakopsora pachyrhizi, Phellinus igniarus, Phialophora spp, Phoma spp,
  • the compounds of formula (I) can also be used to combat and control infestations of insect pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera,
  • Dictyoptera Coleoptera, Siphonaptera, Hymenoptera and Isoptera and also other invertebrate pests, for example, acarine, nematode and mollusc pests.
  • Insects, acarines, nematodes and molluscs are hereinafter collectively referred to as pests.
  • the pests which may be combated and controlled by the use of the invention compounds include those pests associated with agriculture (which term includes the growing of crops for food and fiber products), horticulture and animal husbandry, companion animals, forestry and the storage of products of vegetable origin (such as fruit, grain and timber); those pests associated with the damage of man-made structures and the transmission of diseases of man and animals; and also nuisance pests (such as flies).
  • the compounds of the invention may be used for example on turf, ornamentals, such as flowers, shrubs, broad-leaved trees or evergreens, for example conifers, as well as for tree injection, pest management and the like.
  • Haematopinus spp. Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; from the order Coleoptera, for example,
  • Cimex spp. Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Lep- tocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotino- phara spp. and Triatoma spp.;
  • Blatta spp. Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.; from the order Psocoptera, for example,
  • Thysanoptera for example
  • nematodes for example root knot nematodes, stem eelworms and foliar nematodes;
  • Heterodera spp. for example Heterodera schachtii, Heterodora avenae and Heterodora trifolii
  • Globodera spp. for example Globodera rostochiensis
  • Meloidogyne spp. for example Meloidogyne incoginita and Meloidogyne javanica
  • Radopholus spp. for example Radopholus similis
  • Pratylenchus for example Pratylenchus neglectans and Pratylenchus penetrans
  • Tylenchulus for example Tylenchulus semipenetrans
  • cabbage seedpod weevil (Ceutorhynchus spp.).
  • the compounds of formula I can for example, be used for controlling, i. e. containing or destroying, animal pests of the abovementioned type which occur on useful plants in agriculture, in horticulture and in forests, or on organs of useful plants, such as fruits, flowers, foliage, stalks, tubers or roots, and in some cases even on organs of useful plants which are formed at a later point in time remain protected against these animal pests.
  • target crops and/or useful plants to be protected typically comprise perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St.
  • perennial and annual crops such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries
  • cereals for example barley, maize (corn), millet, oats
  • Augustine grass and Zoysia grass herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber;
  • vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.
  • 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
  • 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 those which naturally are or have been rendered resistant to harmful insects. This includes plants transformed by the use of recombinant DNA techniques, for example, to be capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria. Examples of toxins which can be expressed include ⁇ -endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of bacteria colonising nematodes, and toxins produced by scorpions, arachnids, wasps and fungi.
  • Vip vegetative insecticidal proteins
  • insecticidal proteins of bacteria colonising nematodes and toxins produced by scorpions, arachnids, wasps and fungi.
  • An example of a crop that has been modified to express the Bacillus thuringiensis toxin is the Bt maize KnockOut® (Syngenta Seeds).
  • An example of a crop comprising more than one gene that codes for insecticidal resistance and thus expresses more than one toxin is VipCot® (Syngenta Seeds).
  • Crops or seed material thereof can also be resistant to multiple types of pests (so- called stacked transgenic events when created by genetic modification).
  • a plant can have the ability to express an insecticidal protein while at the same time being herbicide tolerant, for example Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).
  • 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 means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
  • plants refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
  • plant propagation material is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. 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.
  • Pesticidal agents referred to herein using their common name are known, for example, from “The Pesticide Manual”, 15th Ed., British Crop Protection Council 2009.
  • 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.
  • 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 acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenical fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged diphenyl fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, , dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine
  • Suitable additional active ingredients also include the following: 3- difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxylic acid (9-dichloromethylene-1 ,2,3,4- tetrahydro-1 ,4-methano-naphthalen-5-yl)-amide , 3-difluoromethyl-1 -methyl-1 H-pyrazole-4- carboxylic acid methoxy-[1 -methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide , 1 -methyl-3- difluoromethyl-1 H-pyrazole-4-carboxylic acid (2-dichloromethylene-3-ethyl-1 -methyl-indan-4- yl)-amide (1072957-71 -1 ), 1 -methyl-3-difluoromethyl-1 H-pyrazole-4-carboxylic acid (4'- methylsulfanyl-biphenyl-2-yl)-amide, 1 -methyl-3-diflu
  • the compounds of the invention may also be used in combination with anthelmintic agents.
  • anthelmintic agents include, compounds selected from the macrocyclic lactone class of compounds such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin derivatives as described in EP- 357460, EP-444964 and EP-594291 .
  • Additional anthelmintic agents include
  • Additional anthelmintic agents include the benzimidazoles such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, and other members of the class. Additional anthelmintic agents include imidazothiazoles and tetrahydropyrimidines such as tetramisole, levamisole, pyrantel pamoate, oxantel or morantel. Additional anthelmintic agents include flukicides, such as triclabendazole and clorsulon and the cestocides, such as praziquantel and epsiprantel.
  • the compounds of the invention may be used in combination with derivatives and analogues of the paraherquamide/marcfortine class of anthelmintic agents, as well as the antiparasitic oxazolines such as those disclosed in US-5478855, US- 4639771 and DE- 19520936.
  • the compounds of the invention may be used in combination with derivatives and analogues of the general class of dioxomorpholine antiparasitic agents as described in WO- 9615121 and also with anthelmintic active cyclic depsipeptides such as those described in WO-961 1945, WO-9319053, WO- 9325543, EP-626375, EP-382173, WO-9419334, EP- 382173, and EP-503538.
  • the compounds of the invention may be used in combination with other compounds
  • ectoparasiticides for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like;
  • neonicotinoids such as imidacloprid and the like.
  • the compounds of the invention may be used in combination with terpene alkaloids, for example those described in International Patent Application Publication Numbers
  • Organophosphates acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, bromophos, bromophos-ethyl, cadusafos, chlorethoxyphos, chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demeton-S-methyl, demeton-S-methyl sulphone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosthiazate, heptenophos, isazophos, isothioate, isoxathion, malathion, me
  • Carbamates alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801 , isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m- cumenylbutyryl(methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, UC-51717.
  • Arthropod growth regulators a) chitin synthesis inhibitors: benzoylureas:
  • Bacillus thuringiensis Bacillus thuringiensis, bensultap, bifenazate, binapacryl, bromopropylate, BTG-504, BTG- 505, camphechlor, cartap, chlorobenzilate, chlordimeform, chlorfenapyr, chromafenozide, clothianidine, cyromazine, diacloden, diafenthiuron, DBI-3204, dinactin, dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan, ethiprole, ethofenprox, fenazaquin, flumite, MTI- 800, fenpyroximate, fluacrypyrim, flubenzimine, flubrocythrinate, flufenzine, flufenprox, fluproxyfen, halofenprox, hydramethylnon, IKI-220, kanemite, NC-196, neem guard
  • Biological agents Bacillus thuringiensis ssp aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, virus and fungi.
  • Bactericides chlortetracycline, oxytetracycline, streptomycin.
  • Another aspect of invention is related to the use of a compound of formula I or of a preferred individual compound as above-defined, of a composition comprising at least one compound of formula I or at least one preferred individual compound as above-defined, or of a fungicidal or insecticidal mixture comprising at least one compound of formula I or at least one preferred individual compound as above-defined, in admixture with other fungicides or insecticides as described above, for controlling or preventing infestation of plants, e.g. useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living materials by insects or by phytopathogenic
  • microorganisms preferably fungal organisms.
  • a further aspect of invention is related to a method of controlling or preventing an infestation of plants, e.g. useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or of non-living materials by insects or by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, which comprises the application of a compound of formula I or of a preferred individual compound as above-defined as active ingredient to the plants, to parts of the plants or to the locus thereof, to the propagation material thereof, or to any part of the non-living materials.
  • Controlling or preventing means reducing infestation by insects or by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, to such a level that an improvement is demonstrated.
  • a preferred method of controlling or preventing an infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, or insects which comprises the application of a compound of formula I, or an agrochemical composition which contains at least one of said compounds, is foliar application.
  • the frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen or insect.
  • the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field.
  • the compounds of formula I may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
  • a formulation e.g. a composition containing the compound of formula I, and, if desired, a solid or liquid adjuvant or monomers for encapsulating the compound of formula I, may be prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface active
  • 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.
  • rates of 0.001 to 50 g of a compound of formula I per kg of seed preferably from 0.01 to 10g per kg of seed are generally sufficient.
  • compositions of the invention may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK
  • compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects).
  • appropriate formulation inerts diiluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects.
  • conventional slow release formulations may be employed where long lasting efficacy is intended.
  • Particularly formulations to be applied in spraying forms such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g.
  • a seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing
  • Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g. as slow release capsules or microcapsules.
  • the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of at least the compound of formula I together with component (B) and (C), and optionally other active agents, particularly microbiocides or conservatives or the like.
  • Concentrated forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent.
  • Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations.
  • Example 1 This example illustrates the preparation 3-(1 ,1 -dimethyl-2-morpholino-2-oxo- ethyl)-2-(2-isopropoxy-2-phenyl-ethoxy)-5-methyl-6-oxazol-2-yl-thieno[2,3-d]pyrimidin-4-one (Compound l.ad.456) a) Preparation of 2-methyl-2-(5-methyl-6-oxazol-2-yl-2,4-dioxo-1 H-thieno[2,3-d]pyrimidin-3- yi)
  • This acid chloride intermediate was taken up in THF (2 mL) and added slowly to a vigorously stirring THF (5 mL) solution containing triethylamine (0.42 g, 4.18 mmol) and morpholine (0.18 g, 2.09 mmol). After reacting overnight the reaction was quenched with water resulting in precipitate formation. The amorphous wax was collected, washed with water, and dried in the oven at 40°C overnight to deliver 3-(1 ,1 -dimethyl-2-morpholino-2-oxo-ethyl)-5-methyl-6-oxazol-2-yl-1 H- thieno[2,3-d]pyrimidine-2,4-dione. No further purification was performed.
  • R , R , R , X and L are as defined in Table 1.
  • R 1 , R 2 , R 3 , X 1 and L 1 are as defined in Table 1.
  • LC/MS Liquid Chromatography Mass Spectroscopy and the description of the apparatus and the method is: (ACQUITY UPLC from Waters, Phenomenex Gemini C18, 3 ⁇ particle size, 1 10 Angstrom, 30 x 3 mm column, 1 7mL/min., 60 °C, H 2 0 + 0.05% HCOOH (95%) / CH 3 CN/MeOH 4:1 + 0.04% HCOOH (5%) - 2 min.
  • Wettable powders a) b) c) active ingredient [compound of formula (I)] 25 % 50 % 75 % sodium lignosulfonate 5 % 5 %
  • the active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
  • Powders for drv seed treatment a) b) c) active ingredient [compound of formula (I)] 25 % 50 /o 75 %
  • the active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
  • Emulsions of any required dilution which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • Active ingredient [compound of formula (I)] 5 % 6 % 4 % talcum 95 %
  • Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
  • the active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • polyethylene glycol (mol. wt. 200) 3 %
  • the finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
  • nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
  • silicone oil (in the form of a 75 % emulsion in water) 1 %
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • 28 parts of a combination of the compound of formula I are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1 ).
  • This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51 .6 parts of water until the desired particle size is achieved.
  • To this emulsion a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
  • Tomato leaf disks cv. Baby are placed on 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 2 days after application.
  • the inoculated leaf disks are incubated at 23 °C / 21 °C (day/night) and 80% rh under a light regime of 12/12 h (light/dark) in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check disk leaf disks (5 - 7 days after application).
  • Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf disks are inoculated by shaking powdery mildew infected plants above the test plates 1 day after application.
  • the inoculated leaf disks are incubated at 20°C and 60% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate chamber and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check leaf segments (6 - 8 days after application).
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4-5 days after application.
  • nutrient broth PDB potato dextrose broth
  • Mycosphaerella arachidis (Cercospora arachidicola) I liquid culture (early leaf spot)
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4-5 days after application.
  • nutrient broth PDB potato dextrose broth
  • Compound I. ad.456 at 200 ppm gives at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.
  • Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4-5 days after application.
  • nutrient broth PDB potato dextrose broth
  • Compound I. ad.456 at 200 ppm gives at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.
  • Phaeosphaeria nodorum (Septoria nodorum) /wheat / leaf disc preventative (Glume blotch) Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (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 2 days after application.
  • the inoculated test leaf disks are incubated at 20°C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application).
  • 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 / 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).
  • Plasmopara viticola I grape / leaf disc preventative (grape downy mildew)

Abstract

L'invention concerne des composés de formule (I), dans laquelle les substituants sont tels que définis dans la revendication 1, ces composés étant utiles en tant que pesticides.
PCT/EP2014/062884 2013-07-15 2014-06-18 Dérivés hétérobicycliques microbiocides WO2015007453A1 (fr)

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EP13176485 2013-07-15

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CN108368125A (zh) * 2015-10-26 2018-08-03 吉利德阿波罗公司 Acc抑制剂及其用途
US20180362541A1 (en) * 2015-12-09 2018-12-20 Cadent Therapeutics Inc Heteroaromatic nmda receptor modulators and uses thereof
US10500205B2 (en) 2015-12-09 2019-12-10 Cadent Therapeutics, Inc. Thienopyrimidinone NMDA receptor modulators and uses thereof
US10584131B2 (en) 2018-08-03 2020-03-10 Cadent Therapeutics, Inc. Heteroaromatic NMDA receptor modulators and uses thereof
US11274107B2 (en) 2016-12-22 2022-03-15 Cadent Therapeutics, Inc. NMDA receptor modulators and uses thereof

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WO1997002262A1 (fr) * 1995-07-05 1997-01-23 E.I. Du Pont De Nemours And Company Pyrimidinones fongicides
WO2013071169A1 (fr) * 2011-11-11 2013-05-16 Nimbus Apollo, Inc. Inhibiteurs de l'acc et utilisations associées

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
WO1997002262A1 (fr) * 1995-07-05 1997-01-23 E.I. Du Pont De Nemours And Company Pyrimidinones fongicides
WO2013071169A1 (fr) * 2011-11-11 2013-05-16 Nimbus Apollo, Inc. Inhibiteurs de l'acc et utilisations associées

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108368125A (zh) * 2015-10-26 2018-08-03 吉利德阿波罗公司 Acc抑制剂及其用途
US11541057B2 (en) 2015-12-09 2023-01-03 Cadent Therapeutics, Inc. Thienopyrimidinone NMDA receptor modulators and uses thereof
US10500205B2 (en) 2015-12-09 2019-12-10 Cadent Therapeutics, Inc. Thienopyrimidinone NMDA receptor modulators and uses thereof
US10626122B2 (en) 2015-12-09 2020-04-21 Cadent Therapeutics, Inc. Heteroaromatic NMDA receptor modulators and uses thereof
US10973825B2 (en) 2015-12-09 2021-04-13 Cadent Therapeutics, Inc. Thienopyrimidinone NMDA receptor modulators and uses thereof
US11236104B2 (en) 2015-12-09 2022-02-01 Cadent Therapeutics, Inc. Heteroaromatic NMDA receptor modulators and uses thereof
US20180362541A1 (en) * 2015-12-09 2018-12-20 Cadent Therapeutics Inc Heteroaromatic nmda receptor modulators and uses thereof
US11648253B2 (en) 2015-12-09 2023-05-16 Novartis Ag Thienopyrimidinone NMDA receptor modulators and uses thereof
US11274107B2 (en) 2016-12-22 2022-03-15 Cadent Therapeutics, Inc. NMDA receptor modulators and uses thereof
US11807650B2 (en) 2016-12-22 2023-11-07 Novartis Ag NMDA receptor modulators and uses thereof
US10584131B2 (en) 2018-08-03 2020-03-10 Cadent Therapeutics, Inc. Heteroaromatic NMDA receptor modulators and uses thereof
US10752633B2 (en) 2018-08-03 2020-08-25 Cadent Therapeutics, Inc. Heteroaromatic NMDA receptor modulators and uses thereof
US11542264B2 (en) 2018-08-03 2023-01-03 Cadent Therapeutics, Inc. Heteroaromatic NMDA receptor modulators and uses thereof

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