WO2016156085A1 - Microbiocidal heterobicyclic derivatives - Google Patents

Microbiocidal heterobicyclic derivatives Download PDF

Info

Publication number
WO2016156085A1
WO2016156085A1 PCT/EP2016/056127 EP2016056127W WO2016156085A1 WO 2016156085 A1 WO2016156085 A1 WO 2016156085A1 EP 2016056127 W EP2016056127 W EP 2016056127W WO 2016156085 A1 WO2016156085 A1 WO 2016156085A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
halogen
independently selected
cycloalkyi
alkoxy
Prior art date
Application number
PCT/EP2016/056127
Other languages
French (fr)
Inventor
Farhan BOU HAMDAN
Laura Quaranta
Stephan Trah
Matthias Weiss
Original Assignee
Syngenta Participations Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US15/561,788 priority Critical patent/US10273221B2/en
Priority to BR112017020349-9A priority patent/BR112017020349B1/en
Application filed by Syngenta Participations Ag filed Critical Syngenta Participations Ag
Priority to EA201792145A priority patent/EA033690B1/en
Priority to KR1020177026411A priority patent/KR102565369B1/en
Priority to PL16711262T priority patent/PL3274343T3/en
Priority to AU2016239625A priority patent/AU2016239625B2/en
Priority to CN201680018352.7A priority patent/CN107428722B/en
Priority to CN202010122236.8A priority patent/CN111303116B/en
Priority to ES16711262T priority patent/ES2791193T3/en
Priority to MA40816A priority patent/MA40816A1/en
Priority to EP20159778.8A priority patent/EP3683213B1/en
Priority to TNP/2017/000407A priority patent/TN2017000407A1/en
Priority to EP21158139.2A priority patent/EP3848364A1/en
Priority to EP16711262.2A priority patent/EP3274343B1/en
Priority to CR20170418A priority patent/CR20170418A/en
Priority to JP2017550509A priority patent/JP6662901B2/en
Priority to CA2978996A priority patent/CA2978996A1/en
Priority to UAA201710269A priority patent/UA120960C2/en
Priority to MX2017012195A priority patent/MX2017012195A/en
Publication of WO2016156085A1 publication Critical patent/WO2016156085A1/en
Priority to IL254190A priority patent/IL254190B/en
Priority to CONC2017/0009652A priority patent/CO2017009652A2/en

Links

Classifications

    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A01N43/52—1,3-Diazoles; Hydrogenated 1,3-diazoles condensed with carbocyclic rings, e.g. benzimidazoles
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/74—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 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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

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 intermediates useful in the preparation of these heterobicyclic derivatives, to the preparation of these intermediates, to agrochemical compositions which comprise at least one of the heterobicyclic derivatives, to preparation of these compositions and to the 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, in particular fungi.
  • Ri and R 2 are each independently selected from hydrogen, cyano, Ci-C 6 alkyl, C 3 -C 7 cycloalkyl, C 2 -C 6 alkenyl and C 2 -C 6 alkynyl, in which the alkyl, cycloalkyl, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C 6 alkoxy and Ci-C 6 alkylthio; or
  • Ri and R 2 together with the carbon atom to which they are attached represent a C 3 - Cio cycloalkyl group (which may be optionally substituted with 1 to 3 substituents
  • Ci-C 6 alkyl independently selected from the group consisting of halogen, Ci-C 6 alkyl, Ci-C 6 alkoxy and Ci-C 6 alkylthio);
  • R 2 and R 3 together with the carbon atoms to which they are attached represent a C 5 -
  • Cio cycloalkyi (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, Ci-C 6 alkyl, Ci-C 6 alkoxy and Ci-C 6 alkylthio, and, additionally, a ring carbon unit may be replaced by an oxygen or sulphur atom);
  • R 6 is hydrogen, halogen, CrC 6 alkyl or CrC 6 alkoxy
  • each R 7 independently represents hydroxyl, mercapto, cyano, halogen, Ci-C 6 alkyl, Ci-C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkenyl, C 3 -C 6 haloalkynyl, CrC 6 alkylthio, CrC 6 haloalkoxy, Ci-C 6 haloalkylthio, CrC 6 alkoxycarbonyl, CrC 6 alkylcarbonyl, C 3 -C 7 cycloalkyi, CrC 6 alkoxy, C 3 -C 6 alkenyloxy or C 3 -C 6 alkynyloxy; m is 0, 1 , 2, 3 or 4; or
  • R 7 subsitutents together with the carbon atoms to which they are attached represent a C 5 -C 7 cycloalkyi (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, Ci-C 6 alkyl, Ci-C 6 alkoxy and Ci-C 6 alkylthio, and, additionally, a ring carbon unit may be replaced by an oxygen or sulphur atom);
  • R a is selected from hydrogen, Ci-C 6 alkyl, C 3 -C 7 cycloalkyi, C 3 -C 6 alkenyl and C 3 -C 6 alkynyl, in which the alkyl, cycloalkyi, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C 6 alkoxy and Ci-C 6 alkylthio;
  • R b and R c are each independently selected from hydrogen, halogen, cyano, Ci-C 6 alkyl, C 3 -C 7 cycloalkyi, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, CrC 6 alkoxy and CrC 6 alkylthio, in which the alkyl, cycloalkyi, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C 6 alkoxy and Ci-C 6 alkylthio; or a salt or N-oxide thereof.
  • the present invention provides an agrochemical composition comprising a compound of formula (I).
  • Compounds of formula (I) may be used to control phytopathogenic microorganisms.
  • a compound of formula (I), or a composition comprising a compound of formula (I) may be applied directly to the phytopathogen, or to the locus of a phytopathogen, in particular to a plant susceptible to attack by phytopathogens.
  • the present invention provides the use of a compound of formula (I), or a composition comprising a compound of formula (I), as described herein to control a phytopathogen.
  • the present invention provides a method of controlling
  • phytopathogens comprising applying a compound of formula (I), or a composition
  • Compounds of formula (I) are particularly effective in the control of phytopathogenic fungi.
  • the present invention provides the use of a compound of formula (I), or a composition comprising a compound of formula (I), as described herein to control phytopathogenic fungi.
  • the present invention provides a method of controlling
  • phytopathogenic fungi comprising applying a compound of formula (I), or a composition comprising a compound of formula (I), as described herein to said phytopathogenic fungi, or to the locus of said phytopathogenic fungi, in particular to a plant susceptible to attack by phytopathogenic fungi.
  • 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 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 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 groups are aromatic ring systems which can be in mono-, bi- or tricyclic form. Examples of such rings include phenyl, naphthyl, anthracenyl, indenyl or phenanthrenyl. Preferred aryl groups are phenyl and naphthyl, phenyl being most preferred. Where an aryl moiety is said to be substituted, the aryl moiety is preferably substituted by one to four substituents, most preferably by one to three substituents.
  • Heteroaryl groups either alone or as part of a larger group, such as e.g.
  • heteroaryloxy, heteroaryl-alkyl are aromatic ring systems containing at least one heteroatom and consisting either of a single ring or of two or more fused rings.
  • single rings will contain up to three heteroatoms and bicyclic systems up to four heteroatoms which will preferably be chosen from nitrogen, oxygen and sulfur.
  • monocyclic groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl (e.g.
  • [1 ,2,4] triazolyl furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl and thiadiazolyl.
  • bicyclic groups include purinyl, quinolinyl, cinnolinyl, quinoxalinyl, indolyl, indazolyl, benzimidazolyl, benzothiophenyl and benzothiazolyl.
  • heteroaryl groups are preferred, pyridyl being most preferred. Where a heteroaryl moiety is said to be substituted, the heteroaryl moiety is preferably substituted by one to four substituents, most preferably by one to three substituents.
  • Heterocyclyl groups or heterocyclic rings are non-aromatic ring structures containing up to 10 atoms including one or more (preferably one, two or three) heteroatoms selected from O, S and N.
  • Examples of monocyclic groups include, oxetanyl, 4,5-dihydro-isoxazolyl, thietanyl, pyrrolidinyl, tetrahydrofuranyl, [1 ,3]dioxolanyl, piperidinyl, piperazinyl, [1 ,4]dioxanyl, imidazolidinyl, [1 ,3,5]oxadiazinanyl, hexahydro-pyrimidinyl, [1 ,3,5]triazinanyl and morpholinyl or their oxidised versions such as 1 -oxo-thietanyl and 1 ,1 -dioxo-thietanyl.
  • bicyclic groups examples include 2,3-dihydro-benzofuranyl, benzo[1 ,4]dioxolanyl, benzo[1 ,3]dioxolanyl, chromenyl, and 2,3-dihydro-benzo[1 ,4]dioxinyl.
  • a heterocyclyl moiety is said to be substituted, the heterocyclyl moiety is preferably substituted by one to four substituents, most preferably by one to three substituents.
  • 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
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , Ra, Rb, Rc, n and m are, in any combination thereof, as set out below:
  • Ri and R 2 are each independently selected from hydrogen, Ci-C 6 alkyl and C 3 -C 7 cycloalkyl, in which the alkyl and cycloalkyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C 6 alkoxy and Ci-C 6 alkylthio; or R-i and R 2 together with the carbon atom to which they are attached represent a C 3 -C 6 cycloalkyl group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, Ci-C 6 alkyl, Ci-C 6 alkoxy and Ci-C 6 alkylthio).
  • Ri and R 2 are each independently selected from hydrogen and Ci-C 4 alkyl, in which the alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, C1-C3 alkoxy and C1-C3 alkylthio; or R-i and R 2 together with the carbon atom to which they are attached represent a C 3 -C 6 cycloalkyi group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, C1-C3 alkyl, C C 3 alkoxy and C C 3 alkylthio).
  • Ri and R 2 are each independently selected from hydrogen and
  • C1-C4 alkyl in which the alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, methoxy and methylthio; or R-i and R 2 together with the carbon atom to which they are attached represent a C 3 -C 4 cycloalkyi group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen and C C 3 alkyl).
  • R-i and R 2 are each independently selected from hydrogen and Ci-C 3 alkyl; or Ri and R 2 together with the carbon atom to which they are attached represent a C 3 -C 4 cycloalkyi group.
  • Ri and R 2 are each independently selected from hydrogen and C C 3 alkyl; or Ri and R 2 together with the carbon atom to which they are attached represent a C 3 - C 4 cycloalkyi group.
  • R 3 and R 4 are each independently selected from hydrogen, fluoro or
  • Ci-C 3 alkyl or R 3 and R 4 together with the carbon atom to which they are attached represent
  • each R 5 independently represents halogen, cyano, Ci-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 7 cycloalkyi, CrC 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, d-
  • C 6 alkylthio, -C( NOR a )Ci-C 6 alkyl, phenyl, heteroraryl (wherein heteroaryl is pyridyl, thiophenyl, thiazolyl, imidazolyl or oxazolyl), phenoxy or heteroraryloxy (wherein heteroaryl is pyridyl, thiophenyl, thiazolyl, imidazolyl or oxazolyl), in which the alkyl, cycloalkyi, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, phenyl and heteroaryl groups may be optionally substituted with 1 to 5 substituents independently selected from halogen, Ci-C 6 alkyl, Ci-C 6 alkoxy, cyano and Ci-C 6 alkylthio; n is 0, 1 , 2, 3 or 4.
  • each R 5 independently represents halogen, cyano, C 1 -C4 alkyl, C 3 -
  • C 4 cycloalkyi C C 3 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C C 3 alkylthio, - phenyl, heteroraryl (wherein heteroaryl is pyridyl, thiazolyl or oxazolyl), in which the alkyl, cycloalkyi, alkoxy, alkenyloxy, alkynyloxy, phenyl and heteroaryl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen,
  • each R 5 independently represents halogen, cyano, C 1 -C4 alkyl, C 3 -C 4 cycloalkyi or _phenyl, in which the alkyl, cycloalkyi and phenyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen or C C 3 alkyl; n is 0, 1 or 2.
  • each R 5 independently represents halogen, cyano, C C 3 alkyl, C 3 -C 4 cycloalkyi or _phenyl, in which the alkyl, cycloalkyi and phenyl groups may be optionally substituted with 1 to 3 halogen atoms; n is 0, 1 or 2.
  • each R 5 independently represents halogen, C C 3 alkyl or C 3 -C 4 cycloalkyi, in which the alkyl and cycloalkyi groups may be optionally substituted with 1 to 3 fluoro atoms; n is 0, 1 or 2.
  • R 6 is hydrogen, halogen or Ci-C 6 alkyl.
  • R 6 is hydrogen or C C 3 alkyl.
  • R 6 is hydrogen or methyl.
  • R 6 is hydrogen.
  • each R 7 independently represents cyano, halogen, Ci-C 6 alkyl, Ci-C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkenyl, C 3 -C 6 haloalkynyl, CrC 6 alkylthio, Ci-C 6 haloalkoxy, Ci-C 6 haloalkylthio, C 3 -C 7 cycloalkyi, CrC 6 alkoxy, C 3 -C 6 alkenyloxy or Cs- Ce alkynyloxy; m is 0, 1 , 2, 3 or 4; or
  • R 7 substituents together with the carbon atoms to which they are attached represent a C 5 -C 7 cycloalkyi group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, Ci-C 6 alkyl, Ci-C 6 alkoxy and Ci-C 6 alkylthio, and, additionally, a ring carbon unit may be replaced by an oxygen or sulphur atom).
  • each R 7 independently represents cyano, halogen, Ci-C 6 alkyl, Ci-C 6 haloalkyl, C 2 -C 6 alkynyl, CrC 6 alkylthio, CrC 6 haloalkoxy, CrC 6 haloalkylthio, C 3 -C 7 cycloalkyi, Ci-C 6 alkoxy, C 3 -C 6 alkenyloxy or C 3 -C 6 alkynyloxy; m is 0, 1 , 2 or 3; or
  • R 7 substituents together with the carbon atoms to which they are attached represent a C 5 -C 6 cycloalkyi group.
  • each R 7 independently represents cyano, halogen, Ci-C 4 alkyl,
  • each R 7 independently represents cyano, halogen, C C 3 alkyl, Ci-C 3 haloalkyl or C 3 -C 4 cycloalkyi; m is 0, 1 or 2.
  • each R 7 independently represents fluoro, chloro or C C 3 alkyl; m is 1 or 2.
  • R a is selected from hydrogen, Ci-C 6 alkyl, C 3 -C 7 cycloalkyi, C 3 -C 6 alkenyl and C 3 -C 6 alkynyl, in which the alkyl, cycloalkyi, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C 6 alkoxy and Ci-C 6 alkylthio.
  • R a is selected from hydrogen, C C 4 alkyl and C 3 -C 5 cycloalkyi, in which the alkyl and cycloalkyi groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, C C 3 alkoxy and C C 3 alkylthio.
  • R a is selected from hydrogen and C C 4 alkyl, in which the alkyl group may be optionally substituted with 1 to 3 halogen atoms.
  • R a is selected from hydrogen and C C 3 alkyl, in which the alkyl group may be optionally substituted with 1 to 3 fluoro atoms.
  • R b and R c are each independently selected from hydrogen, halogen, cyano, Ci-C 6 alkyl, C 3 -C 7 cycloalkyi, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, CrC 6 alkoxy and CrC 6 alkylthio, in which the alkyl, cycloalkyi, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C 6 alkoxy and Ci-C 6 alkylthio.
  • a preferred group of compounds according to the invention are those of formula IA:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , Ra, Rb, Rc, n and m are as defined for compounds of formula I, or a salt or N-oxide thereof.
  • Preferred definitions of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , Ra, Rb, Rc, n and m are as defined for compounds of formula I .
  • R-i and R 2 are each independently selected from hydrogen, Ci-C 6 alkyi and C 3 -C 7 cycloalkyi, in which the alkyi and cycloalkyi groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, CrC 6 alkoxy and Ci-C 6 alkylthio; or
  • Ri and R 2 together with the carbon atom to which they are attached represent a C 3 -C 6 cycloalkyi group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, Ci-C 6 alkyi, Ci-C 6 alkoxy and Ci-C 6 alkylthio);
  • R 3 and R 4 are each independently selected from hydrogen, halogen, hydroxyl, Ci-C 6 alkyi, CrC 6 alkoxy and C 3 -C 7 cycloalkyi, in which the alkyi, alkoxy and cycloalkyi groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C 6 alkoxy and Ci-C 6 alkylthio; or
  • R 2 and R 3 together with the carbon atoms to which they are attached represent a C 5 - Cj cycloalkyi (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, Ci-C 6 alkyi, Ci-C 6 alkoxy and Ci-C 6 alkylthio, and, additionally, a ring carbon unit may be replaced by an oxygen or sulphur atom);
  • each R 5 independently represents halogen, cyano, Ci-C 6 alkyi, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 7 cycloalkyi, CrC 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, CrC 6 alkylthio, - phenyl, heteroraryl (wherein heteroaryl is pyridyl, thiophenyl, thiazolyl, imidazolyl or oxazolyl), phenoxy or heteroraryloxy (wherein heteroaryl is pyridyl, thiophenyl, thiazolyl, imidazolyl or oxazolyl), in which the alkyi, cycloalkyi, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, phenyl and heteroaryl groups may be optionally substitute
  • R 6 is hydrogen, halogen or CrC 6 alkyl
  • each R 7 independently represents cyano, halogen, Ci-C 6 alkyl, Ci-C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkenyl, C 3 -C 6 haloalkynyl, CrC 6 alkylthio, CrC 6 haloalkoxy, Ci-C 6 haloalkylthio, C 3 -C 7 cycloalkyl, CrC 6 alkoxy, C 3 -C 6 alkenyloxy or C 3 -C 6 alkynyloxy; m is 0, 1 , 2, 3 or 4; or
  • R 7 substituents together with the carbon atoms to which they are attached represent a C 5 -C 7 cycloalkyl group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, Ci-C 6 alkyl, Ci-C 6 alkoxy and Ci-C 6 alkylthio, and, additionally, a ring carbon unit may be replaced by an oxygen or sulphur atom);
  • R a is selected from hydrogen, Ci-C 6 alkyl, C 3 -C 7 cycloalkyl, C 3 -C 6 alkenyl and C 3 -C 6 alkynyl, in which the alkyl, cycloalkyl, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C 6 alkoxy and Ci-C 6 alkylthio;
  • R b and R c are each independently selected from hydrogen, halogen, cyano, Ci-C 6 alkyl, C 3 -C 7 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, CrC 6 alkoxy and CrC 6 alkylthio, in which the alkyl, cycloalkyl, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C 6 alkoxy and Ci-C 6 alkylthio;
  • R-i and R 2 are each independently selected from hydrogen and Ci-C 4 alkyl, in which the alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, C C 3 alkoxy and Ci-C 3 alkylthio; or
  • Ri and R 2 together with the carbon atom to which they are attached represent a C 3 -C 6 cycloalkyl group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, C C 3 alkyl, C C 3 alkoxy and C C 3 alkylthio);
  • R 3 and R 4 are each independently selected from hydrogen, halogen, d-C 4 alkyl and
  • R 6 is hydrogen or C C 3 alkyl
  • each R 7 independently represents cyano, halogen, Ci-C 6 alkyl, Ci-C 6 haloalkyl, C 2 -C 6 alkynyl, CrC 6 alkylthio, CrC 6 haloalkoxy, CrC 6 haloalkylthio, C 3 -C 7 cycloalkyi, CrC 6 alkoxy, C 3 -C 6 alkenyloxy or C 3 -C 6 alkynyloxy; m is 0, 1 , 2 or 3; or
  • R 7 substituents together with the carbon atoms to which they are attached represent a C 5 -C 6 cycloalkyi group
  • R a is selected from hydrogen, C1-C4 alkyl and C 3 -C 5 cycloalkyi, in which the alkyl and cycloalkyi groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, C C 3 alkoxy and C C 3 alkylthio;
  • R-i and R 2 are each independently selected from hydrogen and C1-C4 alkyl, in which the alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, methoxy and methylthio; or
  • Ri and R 2 together with the carbon atom to which they are attached represent a C 3 -C 4 cycloalkyi group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen and C C 3 alkyl);
  • R 3 and R 4 are each independently selected from hydrogen, halogen and C1-C4 alkyl, in which the alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, methoxy and methylthio; or
  • each R 5 independently represents halogen, cyano, C1-C4 alkyl, C 3 -C 4 cycloalkyi or phenyl, in which the alkyl, cycloalkyi and phenyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen or C C 3 alkyl; n is 0, 1 or 2;
  • R 6 is hydrogen or methyl
  • each R 7 independently represents cyano, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C 2 -C 3 alkynyl, C1-C4 alkylthio or C 3 -C 4 cycloalkyi; m is 0, 1 or 2; and R a is selected from hydrogen and C1-C4 alkyl, in which the alkyl group may be optionally substituted with 1 to 3 halogen atoms;
  • Another preferred group of compounds according to the invention are those of formula IE which are compounds of formula I wherein R-i and R 2 are each independently selected from hydrogen and C1-C3 alkyl; or
  • Ri and R 2 together with the carbon atom to which they are attached represent a C 3 -C 4 cycloalkyi group
  • R 3 and R 4 are each independently selected from hydrogen, halogen and C1-C3 alkyl; or
  • each R 5 independently represents halogen, cyano, C1-C3 alkyl, C 3 -C 4 cycloalkyi or phenyl, in which the alkyl, cycloalkyi and phenyl groups may be optionally substituted with 1 to 3 halogen atoms; n is 0, 1 or 2;
  • R 6 is hydrogen or methyl
  • each R 7 independently represents cyano, halogen, C1-C3 alkyl, C1-C3 haloalkyl or C 3 - C 4 cycloalkyi; m is 0, 1 or 2; and
  • R a is selected from hydrogen and C1-C3 alkyl, in which the alkyl group may be optionally substituted with 1 to 3 fluoro atoms;
  • Another preferred group of compounds according to the invention are those of formula IF which are compounds of formula I wherein R-i and R 2 are each independently selected from hydrogen and C1-C3 alkyl; or
  • Ri and R 2 together with the carbon atom to which they are attached represent a C 3 -C 4 cycloalkyi group
  • each R 5 independently represents halogen, C1-C3 alkyl or C 3 -C 4 cycloalkyi, in which the alkyl and cycloalkyi groups may be optionally substituted with 1 to 3 fluoro atoms; n is 0, 1 or 2;
  • R 6 is hydrogen
  • each R 7 independently represents fluoro, chloro or C1-C3 alkyl; m is 1 or 2;
  • Table A1 provides 170 compounds of formula l-a
  • R 6 , R 7 a and R 7 b are all H
  • Table A2 provides 170 compounds of formula la wherein R 7 a and R 7 b are H, R 6 is methyl and wherein the values of R-i , R 2 , R 3 , R 4 and R 5 are as defined in Table Z1 above.
  • Table A3 provides 170 compounds of formula la wherein R 7 a and R 7 b are H, R 6 is Chloro and wherein the values of R-i , R 2 , R 3 , R 4 and R 5 are as defined in Table Z1 above.
  • Table A4 provides 170 compounds of formula la wherein R 6 and R 7 b are H, R 7 a is methyl and wherein the values of R-i , R 2 , R 3 , R 4 and R 5 are as defined in Table Z1 above.
  • Table A5 provides 170 compounds of formula la wherein R 6 and R 7 b are H, R 7 a is fluoro and wherein the values of R-i , R 2 , R 3 , R 4 and R 5 are as defined in Table Z1 above.
  • Table A6 provides 170 compounds of formula la wherein R 6 and R 7 b are H, R 7 a is chloro and wherein the values of R-i , R 2 , R 3 , R 4 and R 5 are as defined in Table Z1 above.
  • Table A7 provides 170 compounds of formula la wherein R 6 and R 7 b are H, R 7 a is ethyl and wherein the values of R-i , R 2 , R 3 , R 4 and R 5 are as defined in Table Z1 above.
  • Table A8 provides 170 compounds of formula la wherein R 6 and R 7 b are H, R 7 a is bromo and wherein the values of R-i , R 2 , R 3 , R 4 and R 5 are as defined in Table Z1 above.
  • Table A9 provides 170 compounds of formula la wherein R 6 is H, R 7 a and R 7 b are methyl and wherein the values of R-i , R 2 , R 3 , R 4 and R 5 are as defined in Table Z1 above.
  • Table A10 provides 170 compounds of formula la wherein R 6 is H, R 7 a and R 7 b are chloro and wherein the values of R-i , R 2 , R 3 , R 4 and R 5 are as defined in Table Z1 above.
  • Table A1 1 provides 170 compounds of formula la wherein R 6 is H, R 7 a is methyl, R 7 b is chloro and wherein the values of R-i , R 2 , R 3 , R 4 and R 5 are as defined in Table Z1 above.
  • Table A12 provides 170 compounds of formula la wherein R 6 is H, R 7 a is fluoro, R 7 b is methyl and wherein the values of R-i , R 2 , R 3 , R 4 and R 5 are as defined in Table Z1 above.
  • Table A13 provides 170 compounds of formula la wherein R 6 is H, R 7 a is fluoro, R 7 b is chloro and wherein the values of R-i , R 2 , R 3 , R 4 and R 5 are as defined in Table Z1 above.
  • Table A14 provides 170 compounds of formula la wherein R 6 is H, R 7 a is methyl, R 7 b is fluoro and wherein the values of R-i , R 2 , R 3 , R 4 and R 5 are as defined in Table Z1 above.
  • Table A15 provides 170 compounds of formula la wherein R 6 is H, R 7 a is chloro, R 7 b is methyl and wherein the values of R-i , R 2 , R 3 , R 4 and R 5 are as defined in Table Z1 above.
  • Table A16 provides 170 compounds of formula la wherein R 6 is H, R 7 a is chloro, R 7 b is fluoro and wherein the values of R-i , R 2 , R 3 , R 4 and R 5 are as defined in Table Z1 above.
  • Table A17 provides 170 compounds of formula la wherein R 6 is H, R 7 a and R 7 b is - CH2CH2CH2- and wherein the values of R-i , R 2 , R 3 , R 4 and R 5 are as defined in Table Z1 above.
  • Table A18 provides 170 compounds of formula la wherein R 6 and R 7 a are H, R 7 b is methyl and wherein the values of R-i , R 2 , R 3 , R 4 and R 5 are as defined in Table Z1 above.
  • Compounds according to the invention may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against diseases that are caused by fungi or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile, improved physico-chemical properties, or increased
  • the compounds of formula I wherein R-i , R 2 , R 3 , R 4 , R 5 , R6, R 7 , m and n are as defined for compounds of formula I, can be obtained by transformation of a compound of formula II, wherein R 6 , R 7 and m are as defined for compounds of formula I, with a compound of formula III, wherein R-i , R 2 , R 3 , R 4 , R 5 and n are as defined for compounds of formula I and Hal is halogen, preferably chloro or bromo, in the presence of an organic base such as triethylamine, ethyldiisopropylamine, pyridine or 2,6-lutidine or in the presence of a transition metal catalyst such as a copper-based catalyst such as copper (I) acetylacetonate or copper (I) bromide-1 ,10-phenanthroline complex, a nickel catalyst such as Dichloro(1 ,3- bis(diphenylphosphino)
  • the compounds of formula IV wherein R-i , R 2 , R 3 , R 4 , R 5 and n are as defined for compounds of formula I, can be obtained by transformation of a compound of formula V, wherein R-i , R 2 , R 3 , R 4 , R 5 and n are as defined for compounds of formula I and R 8 is CrC 6 alkyl, with sodium acetate in acetic acid as described in the literature (Yu. B. Vikharev et al. Pharmaceutical Chemistry Journal, 2005, 39, 405-408). This is shown in Scheme 3.
  • the compounds of formula III wherein R-i, R 2 , R 3 , R 4 , R 5 and n are as defined for compounds of formula I and Hal is halogen, preferably chloro or bromo, can be obtained by transformation of a compound of formula V, wherein R-i, R 2 , R 3 , R 4 , R 5 and n are as defined for compounds of formula I and R 8 is Ci-C 6 alkyi, with a halogenating reagent, such as sulfuryl chloride as described in the literature (Taebo Sim et a!. Tetrahedron Letters, 2010, 51. 4609). This is shown in Scheme 4.
  • Vl-a (Vl-a) (Vl-a) (Vl-a) (Vl-a) (V) (V)
  • R-i , R 2 , R 3 , R 4 , R 5 and n are as defined for compounds of formula I and R' is either H or CrC 6 alkyl, are either commercially available or easily prepared using the methods known by persons who are skilled in the art.
  • the compounds of formula IV wherein R-i , R 2 , R 3 , R 4 , R 5 and n are as defined for compounds of formula I, can be obtained by transformation of a compound of formula VII, wherein R-i , R 2 , R 3 , R 4 , R 5 and n are as defined for compounds of formula I, under acidic conditions, e.g. with sulfuric acid or polyphosphoric acid as described in the literature (Jun-ichi Minamikawa, Bioorganic & Medicinal Chemistry, 2003, 1 1 , 2205-2209). This is shown in Scheme 6.
  • the compounds of formula VII wherein R-i , R 2 , R 3 , R 4 , R 5 and n are as defined for compounds of formula I, can be obtained by transformation of a compound of formula VIII, wherein R-i , R 2 , R 3 , R 4 , R 5 and n are as defined for compounds of formula I, upon treatment with hydroxylamine or hydroxylamine hydrochloride in a solvent such as ethanol or pyridine in the presence or absence of a base such as sodium acetate at temperatures ranging from ambient temperature to heating. This is shown in Scheme 7.
  • the compounds of formula IV wherein R-i , R 2 , R 3 , R 4 , R 5 and n are as defined for compounds of formula I, can be obtained by transformation of a compound of formula IX-a, wherein R-i , R 2 , R 3 , R 4 , R 5 and n are as defined for compounds of formula I, upon treatment with carbonylating agents such as phosgene, triphosgene or carbonyl diimidazole and subsequent heating or utilizing directed catalytic C-H activation - carbonylation in the presence of carbon monoxide gas, a palladium catalyst such as palladium acetate and an oxidant such benzoquinone as reported in the literature (Jaume Granell et al. Chem. Commun., 201 1 , 47, 1054-1056). This is shown in Scheme 8. heme 8
  • the compounds of formula IV wherein R-i , R 2 , R 3 , R 4 , R 5 and n are as defined for compounds of formula I, can be obtained by transformation of a compound of formula IX-b, wherein R-i , R 2 , R 3 , R 4 , R 5 and n are as defined for compounds of formula I and Hal is halogen, preferably chloro, bromo, or iodo, utilizing an intramolecular
  • a palladium catalyst such as Dichlorobis(tricyclohexylphosphine)palladium(ll) or Dichlorobis(triphenlphosphine) palladium(ll) and an organic base such as triethyl amine, pyrrolidine or an inorganic base such cesium carbonte or potassium carbonate as reported in the literature (Ruimao Hua et al. Tetrahedron Letters, 2013, 54, 5159-5161 ). This is shown in Scheme 9.
  • the compounds of formula IV wherein R-i , R 2 , R 3 , R 4 , R 5 and n are as defined for compounds of formula I, can be obtained by transformation of a compound of formula X, wherein R-i , R 2 , R 3 , R 4 , R 5 and n are as defined for compounds of formula I and R 9 is CrC 6 alkyl, under acid conditions e.g. sulfuric acid or triflic acid as described in the literature (Tomohiko Ohwada et al. Journal of Organic Chemistry, 2012, 77, 9313). This is shown in Scheme 10. heme 10
  • DAST diethylaminosulfur trifluoride
  • DFI 2,2-difluoro-1 ,3-dimethyl- imidazolidine
  • halogenating reagent such as phosphorus oxychloride phosphorus oxybromide, thionyl chloride, thionyl bromide or Vilsmeier reagent neat or in the presence a solvent such as dichloromethane at various temperatures ranging form cooling to heating. This is shown in Scheme 13. heme 13
  • an oxidizing agent such as 1 ,1 ,1 -triacetoxy-1 ,1 -dihydro-1 ,2-benziodoxol3(1 H)-one (Des
  • the compounds of formula IV-b wherein R 3 represents hydrogen, R 4 represents OH and R-i , R 2 , R5 and n are as defined for formula I, can be obtained by transformation of a compound of formula IV-c, wherein R 3 represents hydrogen, R 4 represents Hal, wherein Hal is halogen, preferably chloro or bromo, and R-i , R 2 , R5 and n are as defined for formula I, under hydrolysis conditions such as heating in a mixture of an organic solvent such as tetrahydrofuran or 1 ,4-dioxane and water in the presence or absence of an inorganic acid such as hydrochloric acid or an inorganic base such as sodium hydrogencarbonate at temperatures ranging from ambient temperature to heating.
  • an organic solvent such as tetrahydrofuran or 1 ,4-dioxane
  • an inorganic acid such as hydrochloric acid or an inorganic base such as sodium hydrogencarbonate
  • the compounds of formula IV-c wherein R 3 represents hydrogen, R 4 represents Hal, wherein Hal is halogen, preferably chloro or bromo, and R-i , R 2 , R5 and n are as defined for formula I, can be obtained by transformation of a compound of formula IV-d, wherein R 3 and R 4 represent hydrogen and R-i , R 2 , R5 and n are as defined for formula I, with a halogenating agent such as N-chloro succinimide (NCS), N-bromo succinimide (NBS) or 1 ,3-dibromo-5,5- dimethylhydantoin in the presence of a radical initiator such as benzoyl peroxide or azobisisobutyronitrile (AIBN) as described in the literature (Jahangir et al Journal of Organic Chemistry, 1989, 54, 2992). This is shown in Scheme 16.
  • NCS N-chloro succinimide
  • NBS N-bromo succinimide
  • R 3 and R 4 represent Hal, wherein Hal is halogen, preferably chloro or bromo, and R-i , R 2 , R5 and n are as defined for formula I, under hydrolysis conditions such as heating in a mixture of an organic solvent such as tetrahydrofuran or 1 ,4-dioxane and water in the presence or absence of an inorganic acid such as hydrochloric acid or an inorganic base such as sodium hydrogencarbonate at temperatures ranging from ambient temperature to heating.
  • an organic solvent such as tetrahydrofuran or 1 ,4-dioxane
  • an inorganic acid such as hydrochloric acid or an inorganic base such as sodium hydrogencarbonate
  • the compounds of formula IV-e, wherein R 3 and R 4 represent Hal, wherein Hal is halogen, preferably chloro or bromo, and R-i , R 2 , R5 and n are as defined for formula I, can be obtained by transformation of a compound of formula IV-d, wherein R 3 and R 4 represent hydrogen and R-i , R 2 , R 5 and n are as defined for formula I, with a halogenating agent such as N-chloro succinimide (NCS), N-bromo succinimide (NBS) or 1 ,3-dibromo-5,5- dimethylhydantoin in the presence of a radical initiator such as benzoyl peroxide or azobisisobutyronitrile (AIBN) as described in the literature (Jahangir et al Journal of Organic Chemistry, 1989, 54, 2992). This is shown in Scheme 18.
  • NCS N-chloro succinimide
  • NBS N-bromo succinimide
  • R 5 , R 6 , R 7 , m and n are as defined for compounds of formula I , can be obtained by transformation of a compound of formula II, wherein R 6 , R 7 and m are as defined for compounds of formula I, with a compound of formula lll-b, wherein R 3 and R 4 are fluoro and Ri , R2, R5 and n are as defined for formula I and Hal is halogen, preferably chloro or bromo, in the presence of a hindered organic base such as triethylamine, ethyldiisopropylamine, pyridine or 2,6-lutidine or in the presence of a transition metal catalyst such as a copper- based catalyst such as copper (I) acetylacetonate or copper (I) bromide-1 ,10-phenanthroline complex, a nickel catalyst such as Dichloro(1 ,3-bis(diphenylphosphino)propane)nickel or a palladium-based catalyst such
  • the compounds of formula lll-b wherein R 3 and R4 are fluoro and R-i , R 2 , R5 and n are as defined for compounds of formula I and Hal is halogen, preferably chloro or bromo, can be obtained by transformation of a compound of formula IV-f, wherein R 3 and R 4 are fluoro and R-i , R 2 , R5 and n are as defined for compounds of formula I, with a halogenating reagent, such as phosphorus oxychloride phosphorus oxybromide, thionyl chloride, thionyl bromide or Vilsmeier reagent neat or in the presence a solvent such as dichloromethane at various temperatures ranging form cooling to heating. This is shown in Scheme 20.
  • a halogenating reagent such as phosphorus oxychloride phosphorus oxybromide, thionyl chloride, thionyl bromide or Vilsmeier reagent neat or in the presence
  • the compounds of formula IV-f wherein R 3 and R4 are fluoro and R-i , R 2 , R5 and n are as defined for compounds of formula I, can be obtained by transformation of a compound of formula IV-e, wherein R 3 and R 4 are Hal and Hal is halogen, preferably chloro or bromo, and R-i , R 2 , R5 and n are as defined for compounds of formula I, with a fluoride source, such as potassium fluoride, cesium fluoride or hydrogen fluoride in the presence of an organic base such as pyridine or triethylamine as described in the literature (Hideki Umetani et a!. WO 2013047749). This is shown in Scheme 21 .
  • the compounds of formula I wherein R-i , R 2 , R 3 , R 4 , R 5 , R6, R7, m and n are as defined for formula I, can be obtained by transformation of a compound of formula l-d, wherein R-i , R 2 , R 3 , R 4 , R6, R7, m and n are as defined for formula I and Z represents bromine or iodine in a solvent, in the presence of or absence of a base, and in the presence of a coupling reagent and a metal catalyst.
  • the coupling agent, catalyst, solvent and bases provided it is used in ordinary coupling reactions, such as those described in "Cross-Coupling Reactions: A Practical Guide (Topics in Current
  • the compounds of formula I wherein R-i , R 2 , R 3 , R 4 , R 5 , R6, R7, m and n are as defined for formula I, can be obtained by transformation of a compound of formula l-e, wherein R-i , R 2 , R 3 , R 4 , R 5 , R6, m and n are as defined for formula I and Y represents bromine or iodine in a solvent, in the presence of or absence of a base, and in the presence of a coupling reagent and a metal catalyst.
  • the coupling agent, catalyst, solvent and bases provided it is used in ordinary coupling reactions, such as those described in "Cross-Coupling Reactions: A Practical Guide (Topics in Current
  • the compounds of formula I wherein R-i , R 2 , R 3 , R 4 , R 5 , R6, R7, m and n are as defined above can be obtained by transformation of another, closely related, compound of formula I (or an analogue thereof) using standard synthesis techniques known to the person skilled in the art.
  • Non-exhaustive examples include oxidation reactions, reduction reactions, hydrolysis reactions, coupling reactions, aromatic nucleophilic or electrophilic substitution reactions, nucleophilic substitution reactions, nucleophilic addition reactions, and halogenation reactions.
  • 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.
  • 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 compounds of formula I 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
  • the invention could be used to protect non-living materials from fungal attack, e.g. lumber, wall boards and paint.
  • Compounds of formula I and fungicidal compositions containing them may be used to control plant diseases caused by a broad spectrum of fungal plant pathogens. They are effective in controlling a broad spectrum of plant diseases, such as foliar pathogens of ornamental, turf, vegetable, field, cereal, and fruit crops.
  • fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses, which may be controlled 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. including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. comprising 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 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. moniliforme, F. oxysporum, F. proliferatum, F. subglutinans, 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,
  • Trichophyton spp Trichophyton spp, Typhula spp, Uncinula necator, Urocystis spp, Ustilago spp, Venturia spp. including V. inaequalis, Verticillium spp, and Xanthomonas spp.
  • compounds of formula I and fungicidal compositions containing them may be used to control plant diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete, Oomycete and/or Deuteromycete, Blasocladiomycete, Chrytidiomycete, Glomeromycete and/or Mucoromycete classes.
  • pathogens may include:
  • Oomycetes including Phytophthora diseases such as those caused by Phytophthora capsici, Phytophthora infestans, Phytophthora sojae, Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora and Phytophthora erythroseptica; Pythium diseases such as those caused by Pythium
  • Ascomycetes including blotch, spot, blast or blight diseases and/or rots for example those caused by Pleosporales such as Stemphylium solani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phoma destructiva, Phaeosphaeria herpotrichoides, Phaeocryptocus gaeumannii,
  • Pleosporales such as Stemphylium solani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phoma destructiva, Phaeosphaeria herpotrichoides, Phaeocryptocus gaeumannii,
  • Ophiosphaerella graminicola Ophiobolus graminis, Leptosphaeria maculans, Hendersonia creberrima, Helminthosporium triticirepentis, Setosphaeria turcica, Drechslera glycines, Didymella bryoniae, Cycloconium oleagineum, Corynespora cassiicola, Cochliobolus sativus, Bipolaris cactivora, Venturia inaequalis, Pyrenophora teres, Pyrenophora tritici-repentis, Alternaria alternata, Alternaria brassicicola, Alternaria solani and Alternaria tomatophila, Capnodiales such as Septoria tritici, Septoria nodorum, Septoria glycines, Cercospora arachidicola, Cercospora sojina, Cercospora zeae-maydis, Cercosporella capsellae and
  • Microdochium nivale Monilinia fructicola, Monographella albescens, Monosporascus cannonballus, Naemacyclus spp., Ophiostoma novo-ulmi, Paracoccidioides brasiliensis, Penicillium expansum, Pestalotia rhododendri, Petriellidium spp., Pezicula spp., Phialophora gregata, Phyllachora pomigena, Phymatotrichum omnivora, Physalospora abdita,
  • Botryosphaeriales such as Dothiorella aromatica, Diplodia seriata, Guignardia bidwellii, Botrytis cinerea, Botryotinia allii, Botryotinia fabae, Fusicoccum amygdali, Lasiodiplodia theobromae, Macrophoma theicola, Macrophomina phaseolina, Phyllosticta
  • cucurbitacearum cucurbitacearum
  • anthracnoses for example those caused by Glommerelales such as Colletotrichum gloeosporioides, Colletotrichum lagenarium, Colletotrichum gossypii,
  • Gerlachia nivale Gibberella fujikuroi
  • Gibberella zeae Gibberella zeae
  • Gliocladium spp. Myrothecium verrucaria
  • Nectria ramulariae Trichoderma viride
  • Trichothecium roseum Trichothecium roseum
  • Verticillium theobromae Myrothecium verrucaria
  • Basidiomycetes including smuts for example those caused by Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, rusts for example those caused by Pucciniales such as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata, Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp.
  • Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae
  • rusts for example those caused by Pucciniales such as Cerotelium fici, Chr
  • Puccinia striiformis f.sp. Secalis Pucciniastrum coryli, or Uredinales such as Cronartium ribicola, Gymnosporangium juniperi-viginianae, Melampsora medusae, Phakopsora pachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzschelia discolor and Uromyces viciae-fabae; and other rots and diseases such as those caused by Cryptococcus spp., Exobasidium vexans, Marasmiellus inoderma, Mycena spp., Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisum, Laetisaria fuciformis, Waitea circinata, Rhizoctonia solani, Tha
  • Blastocladiomycetes such as Physoderma maydis.
  • Mucoromycetes such as Choanephora cucurbitarum.; Mucor spp.; Rhizopus arrhizus,
  • the compounds and compositions comprising them may also have activity against bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Strptomyces scabies and other related species as well as certain protozoa.
  • 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.
  • 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
  • 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.
  • Toxins that can be expressed by transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as ⁇ -endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp.
  • insecticidal proteins from Bacillus cereus or Bacillus popilliae such as ⁇ -endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect- specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors;
  • ribosome-inactivating proteins such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP- glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
  • RIP ribosome-inactivating proteins
  • ⁇ - endotoxins for example CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins.
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ).
  • Truncated toxins for example a truncated CrylAb, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • amino acid replacements preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see
  • WO03/018810 More examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO93/07278, W095/34656, EP-A-0 427 529, EP-A-451 878 and WO03/052073.
  • Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651 .
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
  • Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a Cry1 Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1 Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses
  • transgenic crops are:
  • MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B- 1 150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
  • NK603 ⁇ MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • 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.
  • compositions 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.
  • Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations include anti-settling agents and dispersing agents and may further include a wetting agent to enhance activity as well an anti-foam and a crystal growth inhibitor. In use, these concentrates are diluted in water and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
  • Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers.
  • the particles contain the active ingredient retained in a solid matrix.
  • Typical solid matrices include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.
  • Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
  • Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required.
  • Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound.
  • Granular formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils
  • Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.
  • Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates.
  • Encapsulated droplets are typically 1 to 50 microns in diameter.
  • the enclosed liquid typically constitutes 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound.
  • Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores.
  • Granules typically range from 1 millimetre to 1 centimetre and preferably 1 to 2 millimetres in diameter. Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring.
  • Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene- butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
  • Pressurised sprayers wherein the active ingredient is dispersed in finely-divided form as a result of vaporisation of a low boiling dispersant solvent carrier, may also be used.
  • Suitable agricultural adjuvants and carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to those skilled in the art.
  • Liquid carriers that can be employed include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, ⁇ , ⁇ -dimethyl formamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glyco
  • Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller's earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.
  • a broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application. These agents, when used, normally comprise from 0.1 % to 15% by weight of the formulation. They can be anionic, cationic, non-ionic or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes.
  • Typical surface active agents include salts of alkyl sulfates, such as
  • alkylarylsulfonate salts such as calcium
  • dodecylbenzenesulfonate alkylphenol-alkylene oxide addition products, such as
  • nonylphenol-C.sub. 18 ethoxylate alcohol-alkylene oxide addition products, such as tridecyl alcohol-C.sub. 16 ethoxylate; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate;
  • quaternary amines such as lauryl trimethylammonium chloride
  • polyethylene glycol esters of fatty acids such as polyethylene glycol stearate
  • block copolymers of ethylene oxide and propylene oxide such as polyethylene glycol stearate
  • salts of mono and dialkyl phosphate esters such as lauryl trimethylammonium chloride
  • adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, anti-foaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and sticking agents.
  • biocidally active ingredients or compositions may be combined with the compositions of the invention and used in the methods of the invention and applied simultaneously or sequentially with the compositions of the invention. When applied simultaneously, these further active ingredients may be formulated together with the compositions of the invention or mixed in, for example, the spray tank. These further biocidally active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.
  • compositions of the invention may also be applied with one or more systemically acquired resistance inducers ("SAR" inducer).
  • SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.
  • the 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 therefore 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.
  • Pyrethroids acrinathin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E) -(1 R)-cis- 2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, bifenthrin, beta - 5 cyfluthrin, cyfluthrin, a-cypermethrin, beta -cypermethrin, bioallethrin, bioallethrin((S)- cyclopentylisomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin, cythithrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, ethofenprox, fenfluthrin, fenpropathrin,
  • Arthropod growth regulators a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox,
  • tebufenozide a compound selected from the group consisting of S-methoprene and S-methoprene.
  • juvenoids pyriproxyfen, methoprene (including S-methoprene), fenoxycarb;
  • lipid biosynthesis inhibitors spirodiclofen.
  • camphechlor cartap
  • chlorobenzilate chlordimeform
  • chlorfenapyr chromafenozide
  • clothianidine cyromazine
  • diacloden diafenthiuron
  • DBI-3204 dinactin
  • protrifenbute protrifenbute, pymethrozine, pyridaben, pyrimidifen, NC-1 1 1 1 , R-195,RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601 , silafluofen, silomadine, spinosad, tebufenpyrad, tetradifon, tetranactin, thiacloprid, thiocyclam, thiamethoxam, tolfenpyrad, triazamate, triethoxyspinosyn, trinactin, verbutin, vertalec, YI-5301 .
  • Bio agents Bacillus thuringiensis ssp aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, virus and fungi.
  • Bactericides chlortetracycline, oxytetracycline, streptomycin.
  • TX means "one compound selected from the group consisting of the compounds described in A1 to A18 (above) of the present invention":
  • an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX,
  • an acaricide selected from the group of substances consisting of 1 ,1 -bis(4-chloro- phenyl)-2-ethoxyethanol (lUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate (lUPAC/Chemical Abstracts name) (1059) + TX, 2-fluoro-/V-methyl-/V-1 -naphthylacetamide (lUPAC name) (1295) + TX, 4-chlorophenyl phenyl sulfone (lUPAC name) (981 ) + TX, abamectin (1 ) + TX, acequinocyl (3) + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, alpha-cypermethrin (202) + TX, amidithion (870) + T
  • oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, parathion (615) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, phenkapton (1330) + TX, phenthoate (631 ) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosphamidon (639) + TX, phoxim (642) + TX, pirimiphos-methyl (652) + TX, polychloroterpenes (traditional name) (1347) + TX, polynactins (alternative name) (653) + TX, proclonol (1350) + TX, profenofos (662) + TX, promacyl (1354) + TX, propargite (671 ) + TX,
  • an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (lUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (lUPAC name) (347) and triphenyltin hydroxide (lUPAC name) (347) + TX,
  • an anthelmintic selected from the group of substances consisting of abamectin (1 ) + TX, crufomate (101 1 ) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291 ) + TX, emamectin benzoate (291 ) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,
  • an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1 122) + TX, fenthion (346) + TX, pyridin-4-amine (lUPAC name) (23) and strychnine (745) + TX,
  • a bactericide selected from the group of substances consisting of 1 -hydroxy-1 /-/- pyridine-2-thione (lUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (lUPAC name) (170) + TX, copper hydroxide (lUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1 105) + TX, dodicin (1 1 12) + TX, fenaminosulf (1 144) + TX, formaldehyde (404) + TX, hydrargaphen (alternative name) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride
  • a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX, Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis (alternative name) (33) + TX, Aphidius colemani (alternative name) (34) + TX, Aphidoletes aphidimyza (alternative name) (35) + TX, Autographa californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide (scientific name) (49) + TX, Bacillus thuringiensis Hopkins (scientific name) (
  • a soil sterilant selected from the group of substances consisting of iodomethane (lUPAC name) (542) and methyl bromide (537) + TX,
  • a chemosterilant selected from the group of substances consisting of apholate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholate [CCN] + TX, morzid [CCN] + TX, penfluron (alternative name) [CCN] + TX, tepa [CCN] + TX, thiohempa (alternative name) [CCN] + TX, thiotepa (alternative name) [CCN] + TX, tretamine
  • an insect pheromone selected from the group of substances consisting of (£)-dec-5- en-1 -yl acetate with (£)-dec-5-en-1 -ol (lUPAC name) (222) + TX, (£)-tridec-4-en-1 -yl acetate (lUPAC name) (829) + TX, (£)-6-methylhept-2-en-4-ol (lUPAC name) (541 ) + TX, (£,Z)- tetradeca-4,10-dien-1 -yl acetate (lUPAC name) (779) + TX, (Z)-dodec-7-en-1 -yl acetate (lUPAC name) (285) + TX, (Z)-hexadec-l 1 -enal (lUPAC name) (436) + TX, (Z)-hexadec-l 1 - en-1 -yl acetate (lUPAC name) (437)
  • an insect repellent selected from the group of substances consisting of 2-(octylthio)- ethanol (lUPAC name) (591 ) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (lUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (lUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1 137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,
  • an insecticide selected from the group of substances consisting of 1 -dichloro-1 - nitroethane (lUPAC/Chemical Abstracts name) (1058) + TX, 1 ,1 -dichloro-2,2-bis(4- ethylphenyl)ethane (lUPAC name) (1056), + TX, 1 ,2-dichloropropane (lUPAC/Chemical Abstracts name) (1062) + TX, 1 ,2-dichloropropane with 1 ,3-dichloropropene (lUPAC name) (1063) + TX, 1 -bromo-2-chloroethane (lUPAC/Chemical Abstracts name) (916) + TX, 2,2,2- trichloro-1 -(3,4-dichlorophenyl)ethyl acetate (lUPAC name) (1451 ) + TX, 2,2-dichlorovinyl 2- ethylsulfinyle
  • pentachlorophenoxide (623) + TX, sodium selenate (lUPAC name) (1401 ) + TX, sodium thiocyanate [CCN] + TX, sophamide (1402) + TX, spinosad (737) + TX, spiromesifen (739) + TX, spirotetrmat (CCN) + TX, sulcofuron (746) + TX, sulcofuron-sodium (746) + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulfuryl fluoride (756) + TX, sulprofos (1408) + TX, tar oils (alternative name) (758) + TX, tau-fluvalinate (398) + TX, tazimcarb (1412) + TX, TDE (1414) + TX, tebufenozide (762) + TX, te
  • a nematicide selected from the group of substances consisting of AKD-3088
  • a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX
  • a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX,
  • a rodenticide selected from the group of substances consisting of 2-isovalerylindan- 1 ,3-dione (lUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891 ) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91 ) + TX, bromethalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorophacinone (140) + TX, cholecalciferol (alternative name) (850) + TX, coumachlor (1004) + TX,
  • a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)- ethyl piperonylate (lUPAC name) (934) + TX, 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2- enone (lUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB- 599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX, an animal repellent selected from the group of substances consisting of
  • a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN] + TX,
  • a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX, and biologically active compounds selected from the group consisting of azaconazole (60207-31 -0] + TX, bitertanol [70585-36-3] + TX, bromuconazole [1 16255-48-2] + TX, cyproconazole [94361 -06-5] + TX, difenoconazole [1 19446-68-3] + TX, diniconazole [83657- 24-3] + TX, epoxiconazole [106325-08-0] + TX, fenbuconazole [1 14369-43-6] + TX, fluquinconazole [136426-54-5] + TX, flusilazole [85509-19-9] + TX, flutriafol [76674
  • a biologically active compound selected from the group consisting of N-[(5-chloro- 35 2-isopropyl-phenyl)methyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1 -methyl-pyrazole-4- carboxamide + TX, 2,6-Dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)- tetrone + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol- 3-amine + TX, 3-(difluoromethyl)-N-(7-fluoro-1 ,1 ,3-trimethyl-indan-4-yl)-1 -methyl-pyrazole-4- carboxamide + TX, CAS 850881 -30-0 +
  • the active ingredient mixture of the compounds of formula I selected from A1 to A18 (above) with active ingredients described above comprises a compound selected from A1 to A18 (above) and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1 :6000, especially from 50:1 to 1 :50, more especially in a ratio of from 20:1 to 1 :20, even more especially from 10:1 to 1 :10, very especially from 5:1 and 1 :5, special preference being given to a ratio of from 2:1 to 1 :2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1 :1 , or 5:1 , or 5:2, or 5:3, or 5:4, or 4:1 , or 4:2, or 4:3, or 3:1 , or 3:2, or 2:1 , or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or
  • the mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.
  • the mixtures comprising a compound of formula I selected from A1 to A18 (above) and one or more active ingredients as described above can be applied, for example, in a single "ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • the order of applying the compounds of formula I selected from A1 to A18 (above) and the active ingredients as described above is not essential for working the present invention.
  • compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
  • auxiliaries such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides
  • compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • 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 compounds (surfactants).
  • extenders for example solvents, solid carriers and, optionally, surface active compounds (surfactants).
  • compositions that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention.
  • Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient.
  • the rate of application per hectare is preferably 1 g to 2000 g of active ingredient per hectare, more preferably 10 to 1000 g/ha, most preferably 10 to 600 g/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.
  • composition comprising a compound of formula (I) according to the present invention is applied either preventative, meaning prior to disease development or curative, meaning after disease development.
  • compositions of the invention may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK
  • compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects).
  • appropriate formulation inerts diiluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects.
  • conventional slow release formulations may be employed where long lasting efficacy is intended.
  • Particularly formulations to be applied in spraying forms such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g.
  • a seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds.
  • suitable seed dressing formulation form e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds.
  • seed dressing formulations are known in the art.
  • Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g. as slow release capsules or microcapsules.
  • the formulations include from 0.01 to 90% by weight of active agent, from
  • 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.
  • LC/MS Liquid Chromatography Mass Spectroscopy and the description of the apparatus and the methods are:
  • 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
  • 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.
  • Wettable powders a) b) c) active ingredient [compound of formula (I)] 25 % 50 % 75 %
  • 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 % 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 active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders 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.
  • 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.
  • 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.
  • Example 1 This example illustrates the preparation of 5-fluoro-3,3,4,4-tetramethyl-1 -(4- methylbenzimidazol-1 -yl)isoquinoline.
  • Step 1 Preparation of ethyl-2-(2-fluorophenyl)-2-methyl-propanoate
  • lanthanum(lll) chloride bis(lithium chloride) complex (0.6 M in THF, 0.50 equiv., 0.12 mol, 207 mL) in tetrahydrofuran (1 .2 M) was stirred at room temperature for 1.5 h. The reaction was then cooled to 0 °C and a solution of methyl magnesium bromide (3.0 M in diethyl ether, 3.0 equiv, 0.74 mol, 248 mL) was subsequently added dropwise. The reaction mixture was stirred at room temperature overnight, cooled to 0 °C and then quenched by the dropwise addition of a saturated aqueous solution of ammonium chloride solution. Water was added and the reaction mixture was stirred for an additional 30 min.
  • Step 3 Preparation of 5-fluoro-3,3,4,4-tetramethyl-1 -methylsulfanyl-isoquinoline.
  • Step 4 Preparation of 5-fluoro-3,3,4,4-tetramethyl-2H-isoquinolin-1 -one.
  • Step 6 Preparation of 5-fluoro-3,3,4,4-tetramethyl-1 -(4-methylbenzimidazol-1 -yl)isoquinoline.
  • Example 2 This example illustrates the preparation of 4,4-difluoro-3,3-dimethyl-1 -(4- methylbenzimidazol-1 -yl)isoquinoline
  • Step 1 Preparation of 3,3-dimethyl-2H-isoquinoline-1 ,4-dione.
  • Step 2 Preparation of 1 -chloro-3,3-dimethyl-isoquinolin-4-one.
  • ⁇ /,/V-dimethylformamide 2.3 mL, 30 mmol
  • dichloromethane 52 mL, 0.6 M
  • oxalyl chloride 0.67 equiv., 20 mmol, 1 .8 mL
  • Step 4 Preparation of 4,4-difluoro-3,3-dimethyl-1 -(4-methylbenzimidazol-1 -yl)isoquinoline.
  • Example 3 This example illustrates the preparation of 1 '-(benzimidazol-1 -yl)-3',3'-dimethyl- spiro(cyclopropane-1 ,4'-isoquinoline)
  • Step 1 Preparation of 3,3-dimethylspiro(2H-isoquinoline-4,1 '-cyclopropane)-1 -one.
  • Step 2 Preparation of 1 '-chloro-3',3'-dimethyl-spiro(cyclopropane-1 ,4'-isoquinoline).
  • oxalyl chloride 1.3 equiv., 0.63 mmol, 0.056 mL
  • dichloromethane (0.8 mL, cone, total 0.25 M) was then added dropwise and the mixture was stirred at room temperature for 1 h.
  • the reaction mixture was poured into an ice-cooled mixture of saturated aqueous NaHC0 3 solution and pentane, and the organic phase was separated.
  • Step 3 Preparation of 1 '-(benzimidazol-1 -yl)-3',3'-dimethyl-spiro(cyclopropane-1 ,4'- isoquinoline).
  • benzimidazole equiv., 0.32 mmol, 38 mg
  • Botryotinia fuckeliana Botryotis cinerea I liquid culture (Gray mould)
  • test compound (Vogels 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 3-4 days after application.
  • DMSO DMSO
  • 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 3-4 days after application.
  • nutrient broth PDB potato dextrose broth
  • Mycelial fragments of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores iss 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
  • 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 measured photometrically 3-4 days after application.
  • nutrient broth PDB potato dextrose broth
  • 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
  • Mvcosphaerella graminicola (Septoria tritici) I liquid culture (Septoria blotch) 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.
  • DMSO DMSO
  • Rice leaf segments cv. Ballila are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf segments are inoculated with a spore suspension of the fungus 2 days after application.
  • the inoculated leaf segments are incubated at 22°C and 80% r.h. 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 segments (5 - 7 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 3-4 days after application.
  • nutrient broth PDB potato dextrose broth
  • Fusarium culmorum I wheat / spikelet preventative (Head blight) Wheat spikelets cv. Monsun are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water.
  • the spikelets are inoculated with a spore suspension of the fungus 1 day after application.
  • the inoculated spikelets are incubated at 20 °C and 60% rh under a light regime of 72 h semi 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 spikelets (6 - 8 days after application).
  • Barley leaf segments cv. Hasso are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water.
  • the leaf segmens are inoculated with a spore suspension of the fungus 2 days after application.
  • the inoculated leaf segments are incubated at 20 °C and 65% 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 disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 - 7 days after application).
  • test compound (Vogels 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 3-4 days after application.
  • DMSO DMSO
  • Sclerotinia sclerotiorum I liquid culture (cottony rot) Mycelia fragments of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (Vogels broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format) the nutrient broth containing the fungal material is added. The test plates are incubated at 24 °C and the inhibition of growth is determined

Abstract

Compounds of the formula (I) wherein the substituents are as defined in claim 1. Furthermore, the present invention relates to agrochemical compositions which comprise compounds of formula (I), to preparation of these compositions, and to the use of the compounds or compositions in agriculture or horticulture for combating, preventing or controlling infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi.

Description

Microbiocidal Heterobicyclic Derivatives
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 intermediates useful in the preparation of these heterobicyclic derivatives, to the preparation of these intermediates, to agrochemical compositions which comprise at least one of the heterobicyclic derivatives, to preparation of these compositions and to the 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, in particular fungi.
Certain fungicidal heterobicyclic compounds are described in WO05070917.
It has now surprisingly been found that certain novel heterobicyclic derivatives have favourable fungicidal properties.
The present invention therefore provides compounds of formula I
Figure imgf000002_0001
wherein
Ri and R2 are each independently selected from hydrogen, cyano, Ci-C6 alkyl, C3-C7 cycloalkyl, C2-C6 alkenyl and C2-C6 alkynyl, in which the alkyl, cycloalkyl, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C6 alkoxy and Ci-C6 alkylthio; or
Ri and R2 together with the carbon atom to which they are attached represent a C3- Cio cycloalkyl group (which may be optionally substituted with 1 to 3 substituents
independently selected from the group consisting of halogen, Ci-C6 alkyl, Ci-C6 alkoxy and Ci-C6 alkylthio);
R3 and R4 are each independently selected from hydrogen, halogen, hydroxyl, Ci-C6 alkyl, CrC6 alkoxy, C3-C7 cycloalkyl, C2-C6 alkenyl and C2-C6 alkynyl, in which the alkyl, alkoxy, cycloalkyl, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C6 alkoxy and Ci-C6 alkylthio; or R3 and R4 together with the carbon atom to which they are attached represent C=0, C=NORa, C=C(Rb)(Rc) or C3-C10 cycloalkyi (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of a halogen, Ci-C6 alkyl, Ci- Ce alkoxy and Ci-C6 alkylthio); or
R2 and R3 together with the carbon atoms to which they are attached represent a C5-
Cio cycloalkyi (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, Ci-C6 alkyl, Ci-C6 alkoxy and Ci-C6 alkylthio, and, additionally, a ring carbon unit may be replaced by an oxygen or sulphur atom);
each R5 independently represents halogen, hydroxyl, mercapto, nitro, cyano, formyl, Ci-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyi, CrC6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, CrC6 alkylthio, -C(=NORa)Ci-C6alkyl, CrC6 alkylcarbonyl, aryl, heteroraryl, aryloxy or heteroraryloxy, in which the alkyl, cycloalkyi, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, aryl and heteroaryl groups may be optionally substituted with 1 to 5 substituents independently selected from halogen, Ci-C6 alkyl, Ci-C6 alkoxy, cyano and Ci-C6 alkylthio; n is 0, 1 , 2, 3 or 4;
R6 is hydrogen, halogen, CrC6 alkyl or CrC6 alkoxy;
each R7 independently represents hydroxyl, mercapto, cyano, halogen, Ci-C6 alkyl, Ci-C6 haloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 haloalkenyl, C3-C6 haloalkynyl, CrC6 alkylthio, CrC6 haloalkoxy, Ci-C6 haloalkylthio, CrC6 alkoxycarbonyl, CrC6 alkylcarbonyl, C3-C7 cycloalkyi, CrC6 alkoxy, C3-C6 alkenyloxy or C3-C6 alkynyloxy; m is 0, 1 , 2, 3 or 4; or
Two adjacent R7 subsitutents together with the carbon atoms to which they are attached represent a C5-C7 cycloalkyi (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, Ci-C6 alkyl, Ci-C6 alkoxy and Ci-C6 alkylthio, and, additionally, a ring carbon unit may be replaced by an oxygen or sulphur atom);
Ra is selected from hydrogen, Ci-C6 alkyl, C3-C7 cycloalkyi, C3-C6 alkenyl and C3-C6 alkynyl, in which the alkyl, cycloalkyi, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C6 alkoxy and Ci-C6 alkylthio;
Rb and Rc are each independently selected from hydrogen, halogen, cyano, Ci-C6 alkyl, C3-C7 cycloalkyi, C2-C6 alkenyl, C2-C6 alkynyl, CrC6 alkoxy and CrC6 alkylthio, in which the alkyl, cycloalkyi, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C6 alkoxy and Ci-C6 alkylthio; or a salt or N-oxide thereof.
In a second aspect the present invention provides an agrochemical composition comprising a compound of formula (I). Compounds of formula (I) may be used to control phytopathogenic microorganisms. Thus, in order to control a phytopathogen a compound of formula (I), or a composition comprising a compound of formula (I), according to the invention may be applied directly to the phytopathogen, or to the locus of a phytopathogen, in particular to a plant susceptible to attack by phytopathogens.
Thus, in a third aspect the present invention provides the use of a compound of formula (I), or a composition comprising a compound of formula (I), as described herein to control a phytopathogen.
In a further aspect the present invention provides a method of controlling
phytopathogens, comprising applying a compound of formula (I), or a composition
comprising a compound of formula (I), as described herein to said phytopathogen, or to the locus of said phytopathogen, in particular to a plant susceptible to attack by a
phytopathogen.
Compounds of formula (I) are particularly effective in the control of phytopathogenic fungi.
Thus, in a yet further aspect the present invention provides the use of a compound of formula (I), or a composition comprising a compound of formula (I), as described herein to control phytopathogenic fungi.
In a further aspect the present invention provides a method of controlling
phytopathogenic fungi, comprising applying a compound of formula (I), or a composition comprising a compound of formula (I), as described herein to said phytopathogenic fungi, or to the locus of said phytopathogenic fungi, in particular to a plant susceptible to attack by phytopathogenic fungi.
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 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, 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 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 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 CCI3CCI2.
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 groups (either alone or as part of a larger group, such as e.g. aryloxy, aryl-alkyl) are aromatic ring systems which can be in mono-, bi- or tricyclic form. Examples of such rings include phenyl, naphthyl, anthracenyl, indenyl or phenanthrenyl. Preferred aryl groups are phenyl and naphthyl, phenyl being most preferred. Where an aryl moiety is said to be substituted, the aryl moiety is preferably substituted by one to four substituents, most preferably by one to three substituents.
Heteroaryl groups (either alone or as part of a larger group, such as e.g.
heteroaryloxy, heteroaryl-alkyl) are aromatic ring systems containing at least one heteroatom and consisting either of a single ring or of two or more fused rings. Preferably, single rings will contain up to three heteroatoms and bicyclic systems up to four heteroatoms which will preferably be chosen from nitrogen, oxygen and sulfur. Examples of monocyclic groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl (e.g.
[1 ,2,4] triazolyl), furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl and thiadiazolyl. Examples of bicyclic groups include purinyl, quinolinyl, cinnolinyl, quinoxalinyl, indolyl, indazolyl, benzimidazolyl, benzothiophenyl and benzothiazolyl.
Monocyclic heteroaryl groups are preferred, pyridyl being most preferred. Where a heteroaryl moiety is said to be substituted, the heteroaryl moiety is preferably substituted by one to four substituents, most preferably by one to three substituents. Heterocyclyl groups or heterocyclic rings (either alone or as part of a larger group, such as heterocyclyl-alkyl) are non-aromatic ring structures containing up to 10 atoms including one or more (preferably one, two or three) heteroatoms selected from O, S and N. Examples of monocyclic groups include, oxetanyl, 4,5-dihydro-isoxazolyl, thietanyl, pyrrolidinyl, tetrahydrofuranyl, [1 ,3]dioxolanyl, piperidinyl, piperazinyl, [1 ,4]dioxanyl, imidazolidinyl, [1 ,3,5]oxadiazinanyl, hexahydro-pyrimidinyl, [1 ,3,5]triazinanyl and morpholinyl or their oxidised versions such as 1 -oxo-thietanyl and 1 ,1 -dioxo-thietanyl. Examples of bicyclic groups include 2,3-dihydro-benzofuranyl, benzo[1 ,4]dioxolanyl, benzo[1 ,3]dioxolanyl, chromenyl, and 2,3-dihydro-benzo[1 ,4]dioxinyl. Where a heterocyclyl moiety is said to be substituted, the heterocyclyl moiety is preferably substituted by one to four substituents, most preferably by one to three substituents.
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 .
It is preferred that the compounds of formula I according to the invention are in free form.
Preferred values of R1, R2, R3, R4, R5, R6, R7, R8, Ra, Rb, Rc, n and m are, in any combination thereof, as set out below:
Preferably Ri and R2 are each independently selected from hydrogen, Ci-C6 alkyl and C3-C7 cycloalkyl, in which the alkyl and cycloalkyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C6 alkoxy and Ci-C6 alkylthio; or R-i and R2 together with the carbon atom to which they are attached represent a C3-C6 cycloalkyl group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, Ci-C6 alkyl, Ci-C6 alkoxy and Ci-C6 alkylthio).
More preferably Ri and R2 are each independently selected from hydrogen and Ci-C4 alkyl, in which the alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, C1-C3 alkoxy and C1-C3 alkylthio; or R-i and R2 together with the carbon atom to which they are attached represent a C3-C6 cycloalkyi group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, C1-C3 alkyl, C C3 alkoxy and C C3 alkylthio).
Even more preferably Ri and R2 are each independently selected from hydrogen and
C1-C4 alkyl, in which the alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, methoxy and methylthio; or R-i and R2 together with the carbon atom to which they are attached represent a C3-C4 cycloalkyi group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen and C C3 alkyl).
More preferably still R-i and R2 are each independently selected from hydrogen and Ci-C3 alkyl; or Ri and R2 together with the carbon atom to which they are attached represent a C3-C4 cycloalkyi group.
Most preferably Ri and R2 are each independently selected from hydrogen and C C3 alkyl; or Ri and R2 together with the carbon atom to which they are attached represent a C3- C4 cycloalkyi group.
Preferably R3 and R4 are each independently selected from hydrogen, halogen, hydroxyl, CrC6 alkyl, CrC6 alkoxy and C3-C7 cycloalkyi, in which the alkyl, alkoxy and cycloalkyi groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C6 alkoxy and Ci-C6 alkylthio; or R3 and R4 together with the carbon atom to which they are attached represent C=0, C=NORa, C=C(Rb)(Rc) or C3-C6 cycloalkyi (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of a halogen, Ci-C6 alkyl, Ci-C6 alkoxy and Ci-C6 alkylthio); or R2 and R3 together with the carbon atoms to which they are attached represent a C5-C7 cycloalkyi (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, Ci-C6 alkyl, Ci-C6 alkoxy and Ci-C6 alkylthio, and, additionally, a ring carbon unit may be replaced by an oxygen or sulphur atom).
More preferably R3 and R4 are each independently selected from hydrogen, halogen, C1-C4 alkyl and C3-C4 cycloalkyi, in which the alkyl and cycloalkyi groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, C C3 alkoxy and Ci-C3 alkylthio; or R3 and R4 together with the carbon atom to which they are attached represent C=0, C=NORa, or C3-C6 cycloalkyi (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of a halogen, C C3 alkyl, d- C3 alkoxy and C C3 alkylthio).
Even more preferably R3 and R4 are each independently selected from hydrogen, halogen and C1-C4 alkyl, in which the alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, methoxy and methylthio; or R3 and R4 together with the carbon atom to which they are attached represent C=0, C=NORa or C3-C4 cycloalkyi (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of a halogen and Ci-C3 alkyl).
More preferably still R3 and R4 are each independently selected from hydrogen, halogen and Ci-C3 alkyl; or R3 and R4 together with the carbon atom to which they are attached represent C=0, C=NORa or C3-C4 cycloalkyi.
Most preferably R3 and R4 are each independently selected from hydrogen, fluoro or
Ci-C3 alkyl; or R3 and R4 together with the carbon atom to which they are attached represent
C=0 or C3-C4 cycloalkyi.
Preferably each R5 independently represents halogen, cyano, Ci-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyi, CrC6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, d-
C6 alkylthio, -C(=NORa)Ci-C6alkyl, phenyl, heteroraryl (wherein heteroaryl is pyridyl, thiophenyl, thiazolyl, imidazolyl or oxazolyl), phenoxy or heteroraryloxy (wherein heteroaryl is pyridyl, thiophenyl, thiazolyl, imidazolyl or oxazolyl), in which the alkyl, cycloalkyi, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, phenyl and heteroaryl groups may be optionally substituted with 1 to 5 substituents independently selected from halogen, Ci-C6 alkyl, Ci-C6 alkoxy, cyano and Ci-C6 alkylthio; n is 0, 1 , 2, 3 or 4.
More preferably each R5 independently represents halogen, cyano, C1-C4 alkyl, C3-
C4 cycloalkyi, C C3 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C C3 alkylthio, -
Figure imgf000008_0001
phenyl, heteroraryl (wherein heteroaryl is pyridyl, thiazolyl or oxazolyl), in which the alkyl, cycloalkyi, alkoxy, alkenyloxy, alkynyloxy, phenyl and heteroaryl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen,
Ci-C3 alkyl and C C3 alkoxy; n is 0, 1 or 2.
Even more preferably each R5 independently represents halogen, cyano, C1-C4 alkyl, C3-C4 cycloalkyi or _phenyl, in which the alkyl, cycloalkyi and phenyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen or C C3 alkyl; n is 0, 1 or 2.
More preferably still each R5 independently represents halogen, cyano, C C3 alkyl, C3-C4 cycloalkyi or _phenyl, in which the alkyl, cycloalkyi and phenyl groups may be optionally substituted with 1 to 3 halogen atoms; n is 0, 1 or 2.
Most preferably each R5 independently represents halogen, C C3 alkyl or C3-C4 cycloalkyi, in which the alkyl and cycloalkyi groups may be optionally substituted with 1 to 3 fluoro atoms; n is 0, 1 or 2.
Preferably R6 is hydrogen, halogen or Ci-C6 alkyl.
More preferably R6 is hydrogen or C C3 alkyl.
Even more preferably R6 is hydrogen or methyl.
Most preferably R6 is hydrogen. Preferably each R7 independently represents cyano, halogen, Ci-C6 alkyl, Ci-C6 haloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 haloalkenyl, C3-C6 haloalkynyl, CrC6 alkylthio, Ci-C6 haloalkoxy, Ci-C6 haloalkylthio, C3-C7 cycloalkyi, CrC6 alkoxy, C3-C6 alkenyloxy or Cs- Ce alkynyloxy; m is 0, 1 , 2, 3 or 4; or
Two adjacent R7 substituents together with the carbon atoms to which they are attached represent a C5-C7 cycloalkyi group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, Ci-C6 alkyl, Ci-C6 alkoxy and Ci-C6 alkylthio, and, additionally, a ring carbon unit may be replaced by an oxygen or sulphur atom).
More preferably each R7 independently represents cyano, halogen, Ci-C6 alkyl, Ci-C6 haloalkyl, C2-C6 alkynyl, CrC6 alkylthio, CrC6 haloalkoxy, CrC6 haloalkylthio, C3-C7 cycloalkyi, Ci-C6 alkoxy, C3-C6 alkenyloxy or C3-C6 alkynyloxy; m is 0, 1 , 2 or 3; or
Two adjacent R7 substituents together with the carbon atoms to which they are attached represent a C5-C6 cycloalkyi group.
Even more preferably each R7 independently represents cyano, halogen, Ci-C4 alkyl,
Ci-C4 haloalkyl, C2-C3 alkynyl, d-C4 alkylthio or C3-C4 cycloalkyi; m is 0, 1 or 2.
More preferably still each R7 independently represents cyano, halogen, C C3 alkyl, Ci-C3 haloalkyl or C3-C4 cycloalkyi; m is 0, 1 or 2.
Most preferably each R7 independently represents fluoro, chloro or C C3 alkyl; m is 1 or 2.
Preferably Ra is selected from hydrogen, Ci-C6 alkyl, C3-C7 cycloalkyi, C3-C6 alkenyl and C3-C6 alkynyl, in which the alkyl, cycloalkyi, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C6 alkoxy and Ci-C6 alkylthio.
More preferably Ra is selected from hydrogen, C C4 alkyl and C3-C5 cycloalkyi, in which the alkyl and cycloalkyi groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, C C3 alkoxy and C C3 alkylthio.
Even more preferably Ra is selected from hydrogen and C C4 alkyl, in which the alkyl group may be optionally substituted with 1 to 3 halogen atoms.
Most preferably Ra is selected from hydrogen and C C3 alkyl, in which the alkyl group may be optionally substituted with 1 to 3 fluoro atoms.
Preferably Rb and Rc are each independently selected from hydrogen, halogen, cyano, Ci-C6 alkyl, C3-C7 cycloalkyi, C2-C6 alkenyl, C2-C6 alkynyl, CrC6 alkoxy and CrC6 alkylthio, in which the alkyl, cycloalkyi, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C6 alkoxy and Ci-C6 alkylthio. A preferred group of compounds according to the invention are those of formula IA:
Figure imgf000010_0001
wherein R1 , R2, R3, R4, R5, R6, R7, R8, Ra, Rb, Rc, n and m are as defined for compounds of formula I, or a salt or N-oxide thereof. Preferred definitions of R1 , R2, R3, R4, R5, R6, R7, R8, Ra, Rb, Rc, n and m are as defined for compounds of formula I .
Another preferred group of compounds according to the invention are those of formula IB which are compounds of formula I wherein R-i and R2 are each independently selected from hydrogen, Ci-C6 alkyi and C3-C7 cycloalkyi, in which the alkyi and cycloalkyi groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, CrC6 alkoxy and Ci-C6 alkylthio; or
Ri and R2 together with the carbon atom to which they are attached represent a C3-C6 cycloalkyi group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, Ci-C6 alkyi, Ci-C6 alkoxy and Ci-C6 alkylthio);
R3 and R4 are each independently selected from hydrogen, halogen, hydroxyl, Ci-C6 alkyi, CrC6 alkoxy and C3-C7 cycloalkyi, in which the alkyi, alkoxy and cycloalkyi groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C6 alkoxy and Ci-C6 alkylthio; or
R3 and R4 together with the carbon atom to which they are attached represent C=0, C=NORa, C=C(Rb)(Rc) or C3-C6 cycloalkyi (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of a halogen, Ci-C6 alkyi, d- C6 alkoxy and Ci-C6 alkylthio); or
R2 and R3 together with the carbon atoms to which they are attached represent a C5- Cj cycloalkyi (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, Ci-C6 alkyi, Ci-C6 alkoxy and Ci-C6 alkylthio, and, additionally, a ring carbon unit may be replaced by an oxygen or sulphur atom);
each R5 independently represents halogen, cyano, Ci-C6 alkyi, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyi, CrC6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, CrC6 alkylthio, -
Figure imgf000010_0002
phenyl, heteroraryl (wherein heteroaryl is pyridyl, thiophenyl, thiazolyl, imidazolyl or oxazolyl), phenoxy or heteroraryloxy (wherein heteroaryl is pyridyl, thiophenyl, thiazolyl, imidazolyl or oxazolyl), in which the alkyi, cycloalkyi, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, phenyl and heteroaryl groups may be optionally substituted with 1 to 5 substituents independently selected from halogen, Ci-C6 alkyl, Ci-C6 alkoxy, cyano and d- C6 alkylthio; n is 0, 1 , 2, 3 or 4;
R6 is hydrogen, halogen or CrC6 alkyl;
each R7 independently represents cyano, halogen, Ci-C6 alkyl, Ci-C6 haloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 haloalkenyl, C3-C6 haloalkynyl, CrC6 alkylthio, CrC6 haloalkoxy, Ci-C6 haloalkylthio, C3-C7 cycloalkyl, CrC6 alkoxy, C3-C6 alkenyloxy or C3-C6 alkynyloxy; m is 0, 1 , 2, 3 or 4; or
Two adjacent R7 substituents together with the carbon atoms to which they are attached represent a C5-C7 cycloalkyl group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, Ci-C6 alkyl, Ci-C6 alkoxy and Ci-C6 alkylthio, and, additionally, a ring carbon unit may be replaced by an oxygen or sulphur atom);
Ra is selected from hydrogen, Ci-C6 alkyl, C3-C7 cycloalkyl, C3-C6 alkenyl and C3-C6 alkynyl, in which the alkyl, cycloalkyl, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C6 alkoxy and Ci-C6 alkylthio;
Rb and Rc are each independently selected from hydrogen, halogen, cyano, Ci-C6 alkyl, C3-C7 cycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, CrC6 alkoxy and CrC6 alkylthio, in which the alkyl, cycloalkyl, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C6 alkoxy and Ci-C6 alkylthio;
or a salt or N-oxide thereof.
Another preferred group of compounds according to the invention are those of formula IC which are compounds of formula I wherein R-i and R2 are each independently selected from hydrogen and Ci-C4 alkyl, in which the alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, C C3 alkoxy and Ci-C3 alkylthio; or
Ri and R2 together with the carbon atom to which they are attached represent a C3-C6 cycloalkyl group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, C C3 alkyl, C C3 alkoxy and C C3 alkylthio);
R3 and R4 are each independently selected from hydrogen, halogen, d-C4 alkyl and
C3-C4 cycloalkyl, in which the alkyl and cycloalkyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, C C3 alkoxy and C C3 alkylthio; or R3 and R4 together with the carbon atom to which they are attached represent C=0, C=NORa, or C3-C6 cycloalkyl (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of a halogen, C C3 alkyl, C C3 alkoxy and Ci-C3 alkylthio); each R5 independently represents halogen, cyano, C1-C4 alkyl, C3-C4 cycloalkyi, d- C3 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C C3 alkylthio, -C(=NORa)Ci-C6alkyl, phenyl, heteroraryl (wherein heteroaryl is pyridyl, thiazolyl or oxazolyl), in which the alkyl, cycloalkyi, alkoxy, alkenyloxy, alkynyloxy, phenyl and heteroaryl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, C C3 alkyl and C C3 alkoxy; n is 0, 1 or 2;
R6 is hydrogen or C C3 alkyl;
each R7 independently represents cyano, halogen, Ci-C6 alkyl, Ci-C6 haloalkyl, C2-C6 alkynyl, CrC6 alkylthio, CrC6 haloalkoxy, CrC6 haloalkylthio, C3-C7 cycloalkyi, CrC6 alkoxy, C3-C6 alkenyloxy or C3-C6 alkynyloxy; m is 0, 1 , 2 or 3; or
Two adjacent R7 substituents together with the carbon atoms to which they are attached represent a C5-C6 cycloalkyi group;
Ra is selected from hydrogen, C1-C4 alkyl and C3-C5 cycloalkyi, in which the alkyl and cycloalkyi groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, C C3 alkoxy and C C3 alkylthio;
or a salt or N-oxide thereof.
Another preferred group of compounds according to the invention are those of formula ID which are compounds of formula I wherein R-i and R2 are each independently selected from hydrogen and C1-C4 alkyl, in which the alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, methoxy and methylthio; or
Ri and R2 together with the carbon atom to which they are attached represent a C3-C4 cycloalkyi group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen and C C3 alkyl);
R3 and R4 are each independently selected from hydrogen, halogen and C1-C4 alkyl, in which the alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, methoxy and methylthio; or
R3 and R4 together with the carbon atom to which they are attached represent C=0, C=NORa or C3-C4 cycloalkyi (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of a halogen and C C3 alkyl);
each R5 independently represents halogen, cyano, C1-C4 alkyl, C3-C4 cycloalkyi or phenyl, in which the alkyl, cycloalkyi and phenyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen or C C3 alkyl; n is 0, 1 or 2;
R6 is hydrogen or methyl;
each R7 independently represents cyano, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C2-C3 alkynyl, C1-C4 alkylthio or C3-C4 cycloalkyi; m is 0, 1 or 2; and Ra is selected from hydrogen and C1-C4 alkyl, in which the alkyl group may be optionally substituted with 1 to 3 halogen atoms;
or a salt or N-oxide thereof.
Another preferred group of compounds according to the invention are those of formula IE which are compounds of formula I wherein R-i and R2 are each independently selected from hydrogen and C1-C3 alkyl; or
Ri and R2 together with the carbon atom to which they are attached represent a C3-C4 cycloalkyi group;
R3 and R4 are each independently selected from hydrogen, halogen and C1-C3 alkyl; or
R3 and R4 together with the carbon atom to which they are attached represent C=0, C=NORa or C3-C4 cycloalkyi;
each R5 independently represents halogen, cyano, C1-C3 alkyl, C3-C4 cycloalkyi or phenyl, in which the alkyl, cycloalkyi and phenyl groups may be optionally substituted with 1 to 3 halogen atoms; n is 0, 1 or 2;
R6 is hydrogen or methyl;
each R7 independently represents cyano, halogen, C1-C3 alkyl, C1-C3 haloalkyl or C3- C4 cycloalkyi; m is 0, 1 or 2; and
Ra is selected from hydrogen and C1-C3 alkyl, in which the alkyl group may be optionally substituted with 1 to 3 fluoro atoms;
or a salt or N-oxide thereof.
Another preferred group of compounds according to the invention are those of formula IF which are compounds of formula I wherein R-i and R2 are each independently selected from hydrogen and C1-C3 alkyl; or
Ri and R2 together with the carbon atom to which they are attached represent a C3-C4 cycloalkyi group;
R3 and R4 are each independently selected from hydrogen, fluoro or C1-C3 alkyl; or R3 and R4 together with the carbon atom to which they are attached represent C=0 or C3-C4 cycloalkyi;
each R5 independently represents halogen, C1-C3 alkyl or C3-C4 cycloalkyi, in which the alkyl and cycloalkyi groups may be optionally substituted with 1 to 3 fluoro atoms; n is 0, 1 or 2;
R6 is hydrogen; and
each R7 independently represents fluoro, chloro or C1-C3 alkyl; m is 1 or 2;
or a salt or N-oxide thereof.
Specific examples of compounds of formula I are illustrated in the Tables A1 to A18 below: Table A1 provides 170 compounds of formula l-a
Figure imgf000014_0001
wherein R6, R7a and R7b are all H
and wherein the values of R-i , R2, R3, R4, and R5 are as defined in Table Z1 below: Table Z1
Figure imgf000014_0002
CH3 CH3 H H 5-0-(pyrid-2-yl)
CH3 CH3 H H 5-CF3
CH3 CH3 H H 5-(2-F-C6H5)
CH3 CH3 H H 5-(thiazol-2-yl)
CH3 CH3 H CH3 H [n=0]
CH3 CH3 H CH3 5-F
CH3 CH3 H OCH3 H [n=0]
CH3 CH3 H OCH3 5-F
CH3 CH3 H F H [n=0]
CH3 CH3 H F 5-F
CH3 CH3 H F 6-F
CH3 CH3 H F 5-CI
CH3 CH3 H F 6-CI
CH3 CH3 H F 5-Br
CH3 CH3 CH3 CH3 H [n=0]
CH3 CH3 CH3 CH3 5-F
CH3 CH3 CH3 CH3 6-F
CH3 CH3 CH3 CH3 7-F
CH3 CH3 CH3 CH3 8-F
CH3 CH3 CH3 CH3 5-CI
CH3 CH3 CH3 CH3 6-CI
CH3 CH3 CH3 CH3 7-CI
CH3 CH3 CH3 CH3 8-CI
CH3 CH3 CH3 CH3 5-Br
CH3 CH3 CH3 CH3 6-Br
CH3 CH3 CH3 CH3 5,6-F2
CH3 CH3 CH3 CH3 5,6-CI2
CH3 CH3 CH3 CH3 5-F-6-CI
CH3 CH3 CH3 CH3 5-CH3
CH3 CH3 CH3 CH3 6-CH3
CH3 CH3 CH3 CH3 5-CH2CH3
CH3 CH3 CH3 CH3 5-cyclopropyl
CH3 CH3 CH3 CH3 5-CN
CH3 CH3 CH3 CH3 5-OC6H5
CH3 CH3 CH3 CH3 5-0-(pyrid-2-yl)
CH3 CH3 CH3 CH3 5-CF3
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000018_0001
167 cyclohexyl F F H [n=0]
168 cyclohexyl H H 5-F
169 cyclohexyl =0 5-F
170 cyclohexyl F F 5-F
Table A2 provides 170 compounds of formula la wherein R7a and R7b are H, R6 is methyl and wherein the values of R-i , R2, R3, R4 and R5 are as defined in Table Z1 above.
Table A3 provides 170 compounds of formula la wherein R7a and R7b are H, R6 is Chloro and wherein the values of R-i , R2, R3, R4 and R5 are as defined in Table Z1 above.
Table A4 provides 170 compounds of formula la wherein R6 and R7b are H, R7a is methyl and wherein the values of R-i , R2, R3, R4 and R5 are as defined in Table Z1 above.
Table A5 provides 170 compounds of formula la wherein R6 and R7b are H, R7a is fluoro and wherein the values of R-i , R2, R3, R4 and R5 are as defined in Table Z1 above.
Table A6 provides 170 compounds of formula la wherein R6 and R7b are H, R7a is chloro and wherein the values of R-i , R2, R3, R4 and R5 are as defined in Table Z1 above.
Table A7 provides 170 compounds of formula la wherein R6 and R7b are H, R7a is ethyl and wherein the values of R-i , R2, R3, R4 and R5 are as defined in Table Z1 above.
Table A8 provides 170 compounds of formula la wherein R6 and R7b are H, R7a is bromo and wherein the values of R-i , R2, R3, R4 and R5 are as defined in Table Z1 above.
Table A9 provides 170 compounds of formula la wherein R6 is H, R7a and R7b are methyl and wherein the values of R-i , R2, R3, R4 and R5 are as defined in Table Z1 above.
Table A10 provides 170 compounds of formula la wherein R6 is H, R7a and R7b are chloro and wherein the values of R-i , R2, R3, R4 and R5 are as defined in Table Z1 above.
Table A1 1 provides 170 compounds of formula la wherein R6 is H, R7a is methyl, R7b is chloro and wherein the values of R-i , R2, R3, R4 and R5 are as defined in Table Z1 above. Table A12 provides 170 compounds of formula la wherein R6 is H, R7a is fluoro, R7b is methyl and wherein the values of R-i , R2, R3, R4 and R5 are as defined in Table Z1 above. Table A13 provides 170 compounds of formula la wherein R6 is H, R7a is fluoro, R7b is chloro and wherein the values of R-i , R2, R3, R4 and R5 are as defined in Table Z1 above.
Table A14 provides 170 compounds of formula la wherein R6 is H, R7a is methyl, R7b is fluoro and wherein the values of R-i , R2, R3, R4 and R5 are as defined in Table Z1 above. Table A15 provides 170 compounds of formula la wherein R6 is H, R7a is chloro, R7b is methyl and wherein the values of R-i , R2, R3, R4 and R5 are as defined in Table Z1 above. Table A16 provides 170 compounds of formula la wherein R6 is H, R7a is chloro, R7b is fluoro and wherein the values of R-i , R2, R3, R4 and R5 are as defined in Table Z1 above. Table A17 provides 170 compounds of formula la wherein R6 is H, R7a and R7b is - CH2CH2CH2- and wherein the values of R-i , R2, R3, R4 and R5 are as defined in Table Z1 above.
Table A18 provides 170 compounds of formula la wherein R6 and R7a are H, R7b is methyl and wherein the values of R-i , R2, R3, R4 and R5 are as defined in Table Z1 above.
Compounds according to the invention may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against diseases that are caused by fungi or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile, improved physico-chemical properties, or increased
biodegradability).
Compounds of the present invention can be made as shown in the following schemes, in which, unless otherwise stated, the definition of each variable is as defined above for a compound of formula (I).
The compounds of formula I, wherein R-i , R2, R3, R4, R5, R6, R7, m and n are as defined for compounds of formula I, can be obtained by transformation of a compound of formula II, wherein R6, R7 and m are as defined for compounds of formula I, with a compound of formula III, wherein R-i , R2, R3, R4, R5 and n are as defined for compounds of formula I and Hal is halogen, preferably chloro or bromo, in the presence of an organic base such as triethylamine, ethyldiisopropylamine, pyridine or 2,6-lutidine or in the presence of a transition metal catalyst such as a copper-based catalyst such as copper (I) acetylacetonate or copper (I) bromide-1 ,10-phenanthroline complex, a nickel catalyst such as Dichloro(1 ,3- bis(diphenylphosphino)propane)nickel or a palladium-based catalyst such as Chloro(2- dicyclohexylphosphino-2',4',6'-triisopropyl-1 ,1 '-biphenyl)[2-(2'-amino-1 ,1 '- biphenyl)]palladium(ll), X-Phos aminobiphenyl palladium chloride precatalyst or [1 ,3-Bis(2,6- Diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(ll) dichloride in an aprotic solvent such as pyridine, toluene or Ν,Ν-dimethylformamide while heating. This is shown in Scheme 1 .
Scheme 1
Figure imgf000021_0001
The compounds of formula II, wherein R6, R7 and m are as defined for compounds of formula I, are either commercially available or easily prepared using the methods known by persons who are skilled in the art as described in the literature (Grimmet, M. R. In Imidazole and Benzimidazole Synthesis; Meth-Cohn, Katritzky,Eds.; Elsevier Science: Oxford, 1997).
The compounds of formula III, wherein R-i , R2, R3, R4, R5 and n are as defined for compounds of formula I and Hal is halogen, preferably chloro or bromo, can be obtained by transformation of a compound of formula IV, wherein R-i , R2, R3, R4, R5 and n are as defined for compounds of formula I, with a halogenating reagent, such as phosphorus oxychloride phosphorus oxybromide, thionyl chloride, thionyl bromide or Vilsmeier reagent neat or in the presence a solvent such as dichloromethane at various temperatures ranging form cooling to heating. This is shown in Scheme 2. heme 2
Figure imgf000021_0002
(IV) (III)
The compounds of formula IV, wherein R-i , R2, R3, R4, R5 and n are as defined for compounds of formula I, can be obtained by transformation of a compound of formula V, wherein R-i , R2, R3, R4, R5 and n are as defined for compounds of formula I and R8 is CrC6 alkyl, with sodium acetate in acetic acid as described in the literature (Yu. B. Vikharev et al. Pharmaceutical Chemistry Journal, 2005, 39, 405-408). This is shown in Scheme 3.
Scheme 3
Figure imgf000022_0001
(V) (IV)
Alternatively, the compounds of formula III, wherein R-i, R2, R3, R4, R5 and n are as defined for compounds of formula I and Hal is halogen, preferably chloro or bromo, can be obtained by transformation of a compound of formula V, wherein R-i, R2, R3, R4, R5 and n are as defined for compounds of formula I and R8 is Ci-C6 alkyi, with a halogenating reagent, such as sulfuryl chloride as described in the literature (Taebo Sim et a!. Tetrahedron Letters, 2010, 51. 4609). This is shown in Scheme 4. Scheme 4
Figure imgf000022_0002
(V) (III)
The compounds of formula V, wherein R-i, R2, R3, R4, R5 and n are as defined for compounds of formula I and R8 is CrC6 alkyi, can be obtained by transformation of a compound of formula Vl-a, Vl-b or Vl-c, wherein R-i, R2, R3, R4, R5 and n are as defined for compounds of formula I and R' is either H or CrC6 alkyi, with a CrC6 alkyi thiocyanate under acidic conditions, e.g. with sulfuric acid as described in the literature (Yu. B. Vikharev et al. Pharmaceutical Chemistry Journal, 2005, 39, 405-408). This is shown in Scheme 5. Scheme 5
Figure imgf000022_0003
(Vl-a) (Vl-a) (Vl-a) (V) The compounds of formula Vl-a, Vl-b or Vl-c, wherein R-i , R2, R3, R4, R5 and n are as defined for compounds of formula I and R' is either H or CrC6 alkyl, are either commercially available or easily prepared using the methods known by persons who are skilled in the art.
Alternatively, the compounds of formula IV, wherein R-i , R2, R3, R4, R5 and n are as defined for compounds of formula I, can be obtained by transformation of a compound of formula VII, wherein R-i , R2, R3, R4, R5 and n are as defined for compounds of formula I, under acidic conditions, e.g. with sulfuric acid or polyphosphoric acid as described in the literature (Jun-ichi Minamikawa, Bioorganic & Medicinal Chemistry, 2003, 1 1 , 2205-2209). This is shown in Scheme 6.
Scheme 6
Figure imgf000023_0001
The compounds of formula VII, wherein R-i , R2, R3, R4, R5 and n are as defined for compounds of formula I, can be obtained by transformation of a compound of formula VIII, wherein R-i , R2, R3, R4, R5 and n are as defined for compounds of formula I, upon treatment with hydroxylamine or hydroxylamine hydrochloride in a solvent such as ethanol or pyridine in the presence or absence of a base such as sodium acetate at temperatures ranging from ambient temperature to heating. This is shown in Scheme 7.
Scheme 7
Figure imgf000023_0002
(VIII) (VII)
The compounds of formula VIII, wherein R-i , R2, R3, R4, R5 and n are as defined for compounds of formula I, are either commercially available or easily prepared using the methods known by persons who are skilled in the art.
Alternatively, the compounds of formula IV, wherein R-i , R2, R3, R4, R5 and n are as defined for compounds of formula I, can be obtained by transformation of a compound of formula IX-a, wherein R-i , R2, R3, R4, R5 and n are as defined for compounds of formula I, upon treatment with carbonylating agents such as phosgene, triphosgene or carbonyl diimidazole and subsequent heating or utilizing directed catalytic C-H activation - carbonylation in the presence of carbon monoxide gas, a palladium catalyst such as palladium acetate and an oxidant such benzoquinone as reported in the literature (Jaume Granell et al. Chem. Commun., 201 1 , 47, 1054-1056). This is shown in Scheme 8. heme 8
Figure imgf000024_0001
(DC-a) (IV)
Alternatively, the compounds of formula IV, wherein R-i , R2, R3, R4, R5 and n are as defined for compounds of formula I, can be obtained by transformation of a compound of formula IX-b, wherein R-i , R2, R3, R4, R5 and n are as defined for compounds of formula I and Hal is halogen, preferably chloro, bromo, or iodo, utilizing an intramolecular
aminocarbonylation in the presence of carbon monoxide gas, a palladium catalyst such as Dichlorobis(tricyclohexylphosphine)palladium(ll) or Dichlorobis(triphenlphosphine) palladium(ll) and an organic base such as triethyl amine, pyrrolidine or an inorganic base such cesium carbonte or potassium carbonate as reported in the literature (Ruimao Hua et al. Tetrahedron Letters, 2013, 54, 5159-5161 ). This is shown in Scheme 9.
Scheme 9
Figure imgf000024_0002
(IX-b) (IV)
Alternatively, the compounds of formula IV, wherein R-i , R2, R3, R4, R5 and n are as defined for compounds of formula I, can be obtained by transformation of a compound of formula X, wherein R-i , R2, R3, R4, R5 and n are as defined for compounds of formula I and R9 is CrC6 alkyl, under acid conditions e.g. sulfuric acid or triflic acid as described in the literature (Tomohiko Ohwada et al. Journal of Organic Chemistry, 2012, 77, 9313). This is shown in Scheme 10. heme 10
Figure imgf000025_0001
The compounds of formula l-b, wherein R3 and R4 are fluoro and R-i , R2, R5, R6, R7, m and n are as defined for compounds of formula I, can be obtained by transformation of a compound of formula l-c wherein R3 and R4 together with the carbon atom to which they are attached represent C=0 and R-i , R2, R5, R6, R7, m and n are as defined for formula I with a fluorinating agent such as diethylaminosulfur trifluoride (DAST) or 2,2-difluoro-1 ,3-dimethyl- imidazolidine (DFI) neat or in the presence of a solvent while heating. This is shown in Scheme 1 1 .
Scheme 1 1
Figure imgf000025_0002
The compounds of formula l-c, wherein R3 and R4 together with the carbon atom to which they are attached represent C=0 and R-i , R2, R5, R6, R7, m and n are as defined for formula I, can be obtained by transformation of a compound of formula II, wherein R6, R7 and m are as defined for compounds of formula I, with a compound of formula lll-a, wherein R3 and R4 together with the carbon atom to which they are attached represent C=0 and R-i , R2, R5 and n are as defined for formula I and Hal is halogen, preferably chloro or bromo, in the presence of a hindered organic base such as triethylamine, ethyldiisopropylamine, pyridine or 2,6-lutidine or in the presence of a transition metal catalyst such as a copper-based catalyst such as copper (I) acetylacetonate or copper (I) bromide-1 ,10-phenanthroline complex, a nickel catalyst such as Dichloro(1 ,3-bis(diphenylphosphino)propane)nickel or a palladium-based catalyst such as Chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1 ,1 '- biphenyl)[2-(2'-amino-1 ,1 '-biphenyl)]palladium(ll), X-Phos aminobiphenyl palladium chloride precatalyst or [1 ,3-Bis(2,6-Diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(ll) dichloride in an aprotic solvent such as pyridine, toluene or Ν,Ν-dimethylformamide while heating. This is shown in Scheme 12.
Scheme 12
Figure imgf000026_0001
(II) ll-a) (l-c)
The compounds of formula lll-a, wherein R3 and R4 together with the carbon atom to which they are attached represent C=0 and R-i , R2, R5 and n are as defined for formula I and Hal is halogen, preferably chloro or bromo, can be obtained by transformation of a compound of formula IV-a, wherein wherein R3 and R4 together with the carbon atom to which they are attached represent C=0 and R-i , R2, R5 and n are as defined for formula I, with a
halogenating reagent, such as phosphorus oxychloride phosphorus oxybromide, thionyl chloride, thionyl bromide or Vilsmeier reagent neat or in the presence a solvent such as dichloromethane at various temperatures ranging form cooling to heating. This is shown in Scheme 13. heme 13
Figure imgf000026_0002
(IV-a) ll-a)
The compounds of formula IV-a, wherein R3 and R4 together with the carbon atom to which they are attached represent C=0 and R-i , R2, R5 and n are as defined for formula I, can be obtained by transformation of a compound of formula IV-b, wherein R3 represents hydrogen, R4 represents OH and R-i , R2, R5 and n are as defined for formula I, with an oxidizing agent such as 1 ,1 ,1 -triacetoxy-1 ,1 -dihydro-1 ,2-benziodoxol3(1 H)-one (Dess-Martin periodinane) or using oxalyl chloride, dimethyl sulfoxide (DMSO) and an organic base, such as triethylamine (Swern oxidation). This is shown in Scheme 14.
Figure imgf000027_0001
The compounds of formula IV-b, wherein R3 represents hydrogen, R4 represents OH and R-i , R2, R5 and n are as defined for formula I, can be obtained by transformation of a compound of formula IV-c, wherein R3 represents hydrogen, R4 represents Hal, wherein Hal is halogen, preferably chloro or bromo, and R-i , R2, R5 and n are as defined for formula I, under hydrolysis conditions such as heating in a mixture of an organic solvent such as tetrahydrofuran or 1 ,4-dioxane and water in the presence or absence of an inorganic acid such as hydrochloric acid or an inorganic base such as sodium hydrogencarbonate at temperatures ranging from ambient temperature to heating. This is shown in Scheme 15.
Figure imgf000027_0002
The compounds of formula IV-c, wherein R3 represents hydrogen, R4 represents Hal, wherein Hal is halogen, preferably chloro or bromo, and R-i , R2, R5 and n are as defined for formula I, can be obtained by transformation of a compound of formula IV-d, wherein R3 and R4 represent hydrogen and R-i , R2, R5 and n are as defined for formula I, with a halogenating agent such as N-chloro succinimide (NCS), N-bromo succinimide (NBS) or 1 ,3-dibromo-5,5- dimethylhydantoin in the presence of a radical initiator such as benzoyl peroxide or azobisisobutyronitrile (AIBN) as described in the literature (Jahangir et al Journal of Organic Chemistry, 1989, 54, 2992). This is shown in Scheme 16.
Figure imgf000028_0001
Alternatively, the compounds of formula IV-a, wherein R3 and R4 together with the carbon atom to which they are attached represent C=0 and R-i , R2, R5 and n are as defined for formula I, can be obtained by transformation of a compound of formula IV-e, wherein R3 and R4 represent Hal, wherein Hal is halogen, preferably chloro or bromo, and R-i , R2, R5 and n are as defined for formula I, under hydrolysis conditions such as heating in a mixture of an organic solvent such as tetrahydrofuran or 1 ,4-dioxane and water in the presence or absence of an inorganic acid such as hydrochloric acid or an inorganic base such as sodium hydrogencarbonate at temperatures ranging from ambient temperature to heating. This is shown in Scheme 17.
Figure imgf000028_0002
The compounds of formula IV-e, wherein R3 and R4 represent Hal, wherein Hal is halogen, preferably chloro or bromo, and R-i , R2, R5 and n are as defined for formula I, can be obtained by transformation of a compound of formula IV-d, wherein R3 and R4 represent hydrogen and R-i , R2, R5 and n are as defined for formula I, with a halogenating agent such as N-chloro succinimide (NCS), N-bromo succinimide (NBS) or 1 ,3-dibromo-5,5- dimethylhydantoin in the presence of a radical initiator such as benzoyl peroxide or azobisisobutyronitrile (AIBN) as described in the literature (Jahangir et al Journal of Organic Chemistry, 1989, 54, 2992). This is shown in Scheme 18.
Scheme 18
Figure imgf000029_0001
The compounds of formula IV-d can be obtained according to the method described in Scheme 3.
Alternatively, the compounds of formula l-a, wherein R3 and R4 are fluoro and R-i , R2,
R5, R6, R7, m and n are as defined for compounds of formula I , can be obtained by transformation of a compound of formula II, wherein R6, R7 and m are as defined for compounds of formula I, with a compound of formula lll-b, wherein R3 and R4 are fluoro and Ri , R2, R5 and n are as defined for formula I and Hal is halogen, preferably chloro or bromo, in the presence of a hindered organic base such as triethylamine, ethyldiisopropylamine, pyridine or 2,6-lutidine or in the presence of a transition metal catalyst such as a copper- based catalyst such as copper (I) acetylacetonate or copper (I) bromide-1 ,10-phenanthroline complex, a nickel catalyst such as Dichloro(1 ,3-bis(diphenylphosphino)propane)nickel or a palladium-based catalyst such as Chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1 ,1 '- biphenyl)[2-(2'-amino-1 ,1 '-biphenyl)]palladium(ll), X-Phos aminobiphenyl palladium chloride precatalyst or [1 ,3-Bis(2,6-Diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(ll) dichloride in an aprotic solvent such as pyridine, toluene or Ν,Ν-dimethylformamide while heating. This is shown in Scheme 19.
Figure imgf000029_0002
The compounds of formula lll-b, wherein R3 and R4 are fluoro and R-i , R2, R5 and n are as defined for compounds of formula I and Hal is halogen, preferably chloro or bromo, can be obtained by transformation of a compound of formula IV-f, wherein R3 and R4 are fluoro and R-i , R2, R5 and n are as defined for compounds of formula I, with a halogenating reagent, such as phosphorus oxychloride phosphorus oxybromide, thionyl chloride, thionyl bromide or Vilsmeier reagent neat or in the presence a solvent such as dichloromethane at various temperatures ranging form cooling to heating. This is shown in Scheme 20.
Scheme 20
Figure imgf000030_0001
(lll-b)
The compounds of formula IV-f, wherein R3 and R4 are fluoro and R-i , R2, R5 and n are as defined for compounds of formula I, can be obtained by transformation of a compound of formula IV-e, wherein R3 and R4 are Hal and Hal is halogen, preferably chloro or bromo, and R-i , R2, R5 and n are as defined for compounds of formula I, with a fluoride source, such as potassium fluoride, cesium fluoride or hydrogen fluoride in the presence of an organic base such as pyridine or triethylamine as described in the literature (Hideki Umetani et a!. WO 2013047749). This is shown in Scheme 21 .
Scheme 21
Figure imgf000030_0002
Alternatively, the compounds of formula I, wherein R-i , R2, R3, R4, R5, R6, R7, m and n are as defined for formula I, can be obtained by transformation of a compound of formula l-d, wherein R-i , R2, R3, R4, R6, R7, m and n are as defined for formula I and Z represents bromine or iodine in a solvent, in the presence of or absence of a base, and in the presence of a coupling reagent and a metal catalyst. There are no particular limitations on the coupling agent, catalyst, solvent and bases, provided it is used in ordinary coupling reactions, such as those described in "Cross-Coupling Reactions: A Practical Guide (Topics in Current
Chemistry)", edited by Norio Miyaura und S.L. Buchwald (editions Springer), or ' Metal- Catalyzed Cross-Coupling Reactions", edited by Armin de Meijere and Frangois Diederich (editions WILEY-VCH). This is shown in Scheme 22.
Figure imgf000031_0001
Alternatively, the compounds of formula I, wherein R-i , R2, R3, R4, R5, R6, R7, m and n are as defined for formula I, can be obtained by transformation of a compound of formula l-e, wherein R-i , R2, R3, R4, R5, R6, m and n are as defined for formula I and Y represents bromine or iodine in a solvent, in the presence of or absence of a base, and in the presence of a coupling reagent and a metal catalyst. There are no particular limitations on the coupling agent, catalyst, solvent and bases, provided it is used in ordinary coupling reactions, such as those described in "Cross-Coupling Reactions: A Practical Guide (Topics in Current
Chemistry)", edited by Norio Miyaura und S.L. Buchwald (editions Springer), or "Metal- Catalyzed Cross-Coupling Reactions", edited by Armin de Meijere and Frangois Diederich (editions WILEY-VCH). This is shown in Scheme 23.
Scheme 23
Figure imgf000031_0002
(l-e) (I)
Alternatively, the compounds of formula I wherein R-i , R2, R3, R4, R5, R6, R7, m and n are as defined above, can be obtained by transformation of another, closely related, compound of formula I (or an analogue thereof) using standard synthesis techniques known to the person skilled in the art. Non-exhaustive examples include oxidation reactions, reduction reactions, hydrolysis reactions, coupling reactions, aromatic nucleophilic or electrophilic substitution reactions, nucleophilic substitution reactions, nucleophilic addition reactions, and halogenation reactions. Certain intermediates described in the above schemes are novel and as such form a further aspect of the invention.
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 fungicide. The term "fungicide" as used herein means a compound that controls, modifies, or prevents the growth of fungi. The term "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.
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 compounds of formula I 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. Compounds of formula I and fungicidal compositions containing them may be used to control plant diseases caused by a broad spectrum of fungal plant pathogens. They are effective in controlling a broad spectrum of plant diseases, such as foliar pathogens of ornamental, turf, vegetable, field, cereal, and fruit crops.
These fungi and fungal vectors of disease, as well as phytopathogenic bacteria and viruses, which may be controlled 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. including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. inclusing 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.
arachidicola, Cercosporidium personatum, Cladosporium spp, Claviceps purpurea,
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. moniliforme, F. oxysporum, F. proliferatum, F. subglutinans, F. solani, Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium spp, Hemileia spp, Histoplasma spp. including H. capsulatum, Laetisaria fuciformis,
Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp, Monilinia spp, Mucor spp, Mycosphaerella spp. including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides spp,
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,
Phomopsis viticola, Phytophthora spp. including P. infestans, Plasmopara spp. including P. halstedii, P. viticola, Pleospora spp., Podosphaera spp. including P. leucotricha, Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp, Pseudoperonospora spp. including P. cubensis, P. humuli, Pseudopeziza tracheiphila, Puccinia Spp. including P. hordei, P. recondita, P. striiformis, P. triticina, Pyrenopeziza spp, Pyrenophora spp, Pyricularia spp. including P. oryzae, Pythium spp. including P. ultimum, Ramularia spp, Rhizoctonia spp, Rhizomucor pusillus, Rhizopus arrhizus, Rhynchosporium spp, Scedosporium spp. including S. apiospermum and S. prolificans, Schizothyrium pomi, Sclerotinia spp, Sclerotium spp, Septoria spp, including S. nodorum, S. tritici, Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix spp, Stagonospora nodorum, Stemphylium spp,. Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia spp, Trichoderma spp. including T. harzianum, T.
pseudokoningii, T. viride,
Trichophyton spp, Typhula spp, Uncinula necator, Urocystis spp, Ustilago spp, Venturia spp. including V. inaequalis, Verticillium spp, and Xanthomonas spp.
In particular, compounds of formula I and fungicidal compositions containing them may be used to control plant diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete, Oomycete and/or Deuteromycete, Blasocladiomycete, Chrytidiomycete, Glomeromycete and/or Mucoromycete classes.
These pathogens may include:
Oomycetes, including Phytophthora diseases such as those caused by Phytophthora capsici, Phytophthora infestans, Phytophthora sojae, Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora and Phytophthora erythroseptica; Pythium diseases such as those caused by Pythium
aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare and Pythium ultimum; diseases caused by Peronosporales such as Peronospora destructor, Peronospora parasitica, Plasmopara viticola, Plasmopara halstedii, Pseudoperonospora cubensis, Albugo Candida, Sclerophthora macrospora and Bremia lactucae; and others such as Aphanomyces cochlioides, Labyrinthula zosterae, Peronosclerospora sorghi and
Sclerospora graminicola.
Ascomycetes, including blotch, spot, blast or blight diseases and/or rots for example those caused by Pleosporales such as Stemphylium solani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phoma destructiva, Phaeosphaeria herpotrichoides, Phaeocryptocus gaeumannii,
Ophiosphaerella graminicola, Ophiobolus graminis, Leptosphaeria maculans, Hendersonia creberrima, Helminthosporium triticirepentis, Setosphaeria turcica, Drechslera glycines, Didymella bryoniae, Cycloconium oleagineum, Corynespora cassiicola, Cochliobolus sativus, Bipolaris cactivora, Venturia inaequalis, Pyrenophora teres, Pyrenophora tritici-repentis, Alternaria alternata, Alternaria brassicicola, Alternaria solani and Alternaria tomatophila, Capnodiales such as Septoria tritici, Septoria nodorum, Septoria glycines, Cercospora arachidicola, Cercospora sojina, Cercospora zeae-maydis, Cercosporella capsellae and Cercosporella herpotrichoides, Cladosporium carpophilum, Cladosporium effusum,
Passalora fulva, Cladosporium oxysporum, Dothistroma septosporum, Isariopsis clavispora, Mycosphaerella fijiensis, Mycosphaerella graminicola, Mycovellosiella koepkeii,
Phaeoisariopsis bataticola, Pseudocercospora vitis, Pseudocercosporella herpotrichoides, Ramularia beticola, Ramularia collo-cygni, Magnaporthales such as Gaeumannomyces graminis, Magnaporthe grisea, Pyricularia oryzae, Diaporthales such as Anisogramma anomala, Apiognomonia errabunda, Cytospora platani, Diaporthe phaseolorum, Discula destructiva, Gnomonia fructicola, Greeneria uvicola, Melanconium juglandinum, Phomopsis viticola, Sirococcus clavigignenti-juglandacearum, Tubakia dryina, Dicarpella spp., Valsa ceratosperma, and others such as Actinothyrium graminis, Ascochyta pisi, Aspergillus flavus, Aspergillus fumigatus, Aspergillus nidulans, Asperisporium caricae, Blumeriella jaapii, Candida spp., Capnodium ramosum, Cephaloascus spp., Cephalosporium gramineum, Ceratocystis paradoxa, Chaetomium spp., Hymenoscyphus pseudoalbidus, Coccidioides spp., Cylindrosporium padi, Diplocarpon malae, Drepanopeziza campestris, Elsinoe ampelina, Epicoccum nigrum, Epidermophyton spp., Eutypa lata, Geotrichum candidum, Gi belli na cerealis, Gloeocercospora sorghi, Gloeodes pomigena, Gloeosporium perennans; Gloeotinia temulenta, Griphospaeria corticola, Kabatiella lini, Leptographium microsporum, Leptosphaerulinia crassiasca, Lophodermium seditiosum, Marssonina graminicola,
Microdochium nivale, Monilinia fructicola, Monographella albescens, Monosporascus cannonballus, Naemacyclus spp., Ophiostoma novo-ulmi, Paracoccidioides brasiliensis, Penicillium expansum, Pestalotia rhododendri, Petriellidium spp., Pezicula spp., Phialophora gregata, Phyllachora pomigena, Phymatotrichum omnivora, Physalospora abdita,
Plectosporium tabacinum, Polyscytalum pustulans, Pseudopeziza medicaginis,
Pyrenopeziza brassicae, Ramulispora sorghi, Rhabdocline pseudotsugae, Rhynchosporium secalis, Sacrocladium oryzae, Scedosporium spp., Schizothyrium pomi, Sclerotinia sclerotiorum, Sclerotinia minor, Sclerotium spp., Typhula ishikariensis, Seimatosporium mariae, Lepteutypa cupressi, Septocyta ruborum, Sphaceloma perseae, Sporonema phacidioides, Stigmina palmivora, Tapesia yallundae, Taphrina bullata, Thielviopsis basicola, Trichoseptoria fructigena, Zygophiala jamaicensis; powdery mildew diseases for example those caused by Erysiphales such as Blumeria graminis, Erysiphe polygoni, Uncinula necator, Sphaerotheca fuligena, Podosphaera leucotricha, Podospaera macularis
Golovinomyces cichoracearum, Leveillula taurica, Microsphaera diffusa, Oidiopsis gossypii, Phyllactinia guttata and Oidium arachidis; molds for example those caused by
Botryosphaeriales such as Dothiorella aromatica, Diplodia seriata, Guignardia bidwellii, Botrytis cinerea, Botryotinia allii, Botryotinia fabae, Fusicoccum amygdali, Lasiodiplodia theobromae, Macrophoma theicola, Macrophomina phaseolina, Phyllosticta
cucurbitacearum; anthracnoses for example those caused by Glommerelales such as Colletotrichum gloeosporioides, Colletotrichum lagenarium, Colletotrichum gossypii,
Glomerella cingulata, and Colletotrichum graminicola; and wilts or blights for example those caused by Hypocreales such as Acremonium strictum, Claviceps purpurea, Fusarium culmorum, Fusarium graminearum, Fusarium virguliforme, Fusarium oxysporum, Fusarium subglutinans, Fusarium oxysporum f.sp. cubense, Gerlachia nivale, Gibberella fujikuroi, Gibberella zeae, Gliocladium spp., Myrothecium verrucaria, Nectria ramulariae, Trichoderma viride, Trichothecium roseum, and Verticillium theobromae.
Basidiomycetes, including smuts for example those caused by Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, rusts for example those caused by Pucciniales such as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata, Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp. Hordei, Puccinia striiformis f.sp. Secalis, Pucciniastrum coryli, or Uredinales such as Cronartium ribicola, Gymnosporangium juniperi-viginianae, Melampsora medusae, Phakopsora pachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzschelia discolor and Uromyces viciae-fabae; and other rots and diseases such as those caused by Cryptococcus spp., Exobasidium vexans, Marasmiellus inoderma, Mycena spp., Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisum, Laetisaria fuciformis, Waitea circinata, Rhizoctonia solani, Thanetephorus cucurmeris, Entyloma dahliae, Entylomella microspora, Neovossia moliniae and Tilletia caries.
Blastocladiomycetes, such as Physoderma maydis.
Mucoromycetes, such as Choanephora cucurbitarum.; Mucor spp.; Rhizopus arrhizus,
As well as diseases caused by other species and genera closely related to those listed above.
In addition to their fungicidal activity, the compounds and compositions comprising them may also have activity against bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Strptomyces scabies and other related species as well as certain protozoa.
Within the scope of present invention, 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. 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. 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 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 δ-endotoxins, vegetative insecticidal proteins (Vip), 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). For example, a plant can have the ability to express an insecticidal protein while at the same time being herbicide tolerant, for example Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International). The 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.
Toxins that can be expressed by transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect- specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors;
ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP- glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
Further, in the context of the present invention there are to be understood by δ- endotoxins, for example CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ). Truncated toxins, for example a truncated CrylAb, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see
WO03/018810). More examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO93/07278, W095/34656, EP-A-0 427 529, EP-A-451 878 and WO03/052073.
The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651 .
The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a Cry1 Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1 Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses a CrylAc toxin); Bollgard II® (cotton variety that expresses a CrylAc and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a Cry1 Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin);
NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt1 1 corn borer (CB) trait) and Protecta®.
Further examples of such transgenic crops are:
1 . Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St.
Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1 Ab toxin. Bt1 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St.
Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CrylAb toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B- 1 150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/ES/96/02.
6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1 160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cry1 F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.
7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de
Tervuren, B-1 150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 χ MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
The term "locus" as used herein means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
The term "plants" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
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.
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, 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.
Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations include anti-settling agents and dispersing agents and may further include a wetting agent to enhance activity as well an anti-foam and a crystal growth inhibitor. In use, these concentrates are diluted in water and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers. The particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.
Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound. Granular formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.
Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.
Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates. Encapsulated droplets are typically 1 to 50 microns in diameter. The enclosed liquid typically constitutes 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound. Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores. Granules typically range from 1 millimetre to 1 centimetre and preferably 1 to 2 millimetres in diameter. Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene- butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
Other useful formulations for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired
concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurised sprayers, wherein the active ingredient is dispersed in finely-divided form as a result of vaporisation of a low boiling dispersant solvent carrier, may also be used.
Suitable agricultural adjuvants and carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to those skilled in the art.
Liquid carriers that can be employed include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, Ν,Ν-dimethyl formamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidinone, ethyl acetate, 2-ethyl hexanol, ethylene carbonate, 1 ,1 ,1 -trichloroethane, 2-heptanone, alpha pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropyl benzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octyl amine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol, glycerine and N-methyl-2-pyrrolidinone. Water is generally the carrier of choice for the dilution of concentrates.
Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller's earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.
A broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application. These agents, when used, normally comprise from 0.1 % to 15% by weight of the formulation. They can be anionic, cationic, non-ionic or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes. Typical surface active agents include salts of alkyl sulfates, such as
diethanolammonium lauryl sulphate; alkylarylsulfonate salts, such as calcium
dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as
nonylphenol-C.sub. 18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C.sub. 16 ethoxylate; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate;
quaternary amines, such as lauryl trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.
Other adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, anti-foaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and sticking agents.
In addition, further, other biocidally active ingredients or compositions may be combined with the compositions of the invention and used in the methods of the invention and applied simultaneously or sequentially with the compositions of the invention. When applied simultaneously, these further active ingredients may be formulated together with the compositions of the invention or mixed in, for example, the spray tank. These further biocidally active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.
In addition, the compositions of the invention may also be applied with one or more systemically acquired resistance inducers ("SAR" inducer). SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.
The 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 therefore 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 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 fungicides, organophosphorous fungicides, organotin fungicides, oxathiin fungicides, oxazole fungicides, phenylsulfamide fungicides, polysulfide fungicides, pyrazole fungicides, pyridine fungicides, pyrimidine fungicides, pyrrole fungicides, quaternary ammonium fungicides, quinoline fungicides, quinone fungicides, quinoxaline fungicides, strobilurin fungicides, sulfonanilide fungicides, thiadiazole fungicides, thiazole fungicides, thiazolidine fungicides, thiocarbamate fungicides, thiophene fungicides, triazine fungicides, triazole fungicides, triazolopyrimidine fungicides, urea fungicides, valinamide fungicides, and zinc fungicides.
Examples of suitable additional active ingredients also include the following: 3- difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxylic acid (9-dichloromethylene-1 ,2,3,4- tetrahydro-1 ,4-methano-naphthalen-5-yl)-amide , 3-difluoromethyl-1 -methyl-1 H-pyrazole-4- carboxylic acid methoxy-[1 -methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide , 1 -methyl-3- difluoromethyl-1 H-pyrazole-4-carboxylic acid (2-dichloromethylene-3-ethyl-1 -methyl-indan-4- yl)-amide (1072957-71 -1 ), 1 -methyl-3-difluoromethyl-1 H-pyrazole-4-carboxylic acid (4'- methylsulfanyl-biphenyl-2-yl)-amide, 1 -methyl-3-difluoromethyl-4H-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, (E)-N-methyl-2- [2- (2, 5-dimethylphenoxymethyl) phenyl]-2-methoxy-iminoacetamide, 4-bromo-2-cyano-N, N-dimethyl-6-trifluoromethylbenzimidazole-1 -sulphonamide, a- [N-(3-chloro-2, 6-xylyl)-2- methoxyacetamido]-y-butyrolactone, 4-chloro-2-cyano-N, - dimethyl-5-p-tolylimidazole-1 - sulfonamide, N-allyl-4, 5,-dimethyl-2-trimethylsilylthiophene-3-carboxamide, N- (l-cyano-1 , 2- dimethylpropyl)-2- (2, 4-dichlorophenoxy) propionamide, N- (2-methoxy-5-pyridyl)- cyclopropane carboxamide, (.+-.)-cis-1 -(4-chlorophenyl)-2-(1 H-1 ,2,4-triazol-1 -yl)- cycloheptanol, 2-(1 -tert-butyl)-1 -(2-chlorophenyl)-3-(1 ,2,4-triazol-1 -yl)-propan-2-ol, 2',6'- dibromo-2-methyl-4-trifluoromethoxy-4'-trifluoromethyl-1 ,3-thiazole- 5-carboxanilide, 1 - imidazolyl-1 -(4'-chlorophenoxy)-3,3-dimethylbutan-2-one, methyl (E)-2-[2-[6-(2- cyanophenoxy)pyrimidin-4-yloxy]phenyl]3-methoxyacrylate, methyl (E)-2-[2-[6-(2- thioamidophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylat e, methyl (E)-2-[2-[6-(2- fluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[6-(2,6- difluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacryla te, methyl (E)-2-[2-[3-(pyrimidin- 2-yloxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[3-(5-methylpyrimidin-2-yloxy)- phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[3-(phenyl- sulphonyloxy)phenoxy]phenyl-3-methoxyacrylate, methyl (E)-2-[2-[3-(4- nitrophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-phenoxyphenyl]-3- methoxyacrylate, methyl (E)-2-[2-(3,5-dimethyl-benzoyl)pyrrol-1 -yl]-3-methoxyacrylate, methyl (E)-2-[2-(3-methoxyphenoxy)phenyl]-3-methoxyacrylate, methyl (E)-2[2-(2- phenylethen-1 -yl)-phenyl]-3-methoxyacrylate, methyl (E)-2-[2-(3,5-dichlorophenoxy)pyridin-3- yl]-3-methoxyacrylate, methyl (E)-2-(2-(3-(1 ,1 ,2,2-tetrafluoroethoxy)phenoxy)phenyl)-3- methoxyacrylate, methyl (E)-2-(2-[3-(alpha-hydroxybenzyl)phenoxy]phenyl)-3- methoxyacrylate, methyl (E)-2-(2-(4-phenoxypyridin-2-yloxy)phenyl)-3-methoxyacrylate, methyl (E)-2-[2-(3-n-propyloxy-phenoxy)phenyl]3-methoxyacrylate, methyl (E)-2-[2-(3- isopropyloxyphenoxy)phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[3-(2- fluorophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-(3- ethoxyphenoxy)phenyl]-3-methoxyacrylate, methyl (E)-2-[2-(4-tert-butyl-pyridin-2- yloxy)phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[3-(3-cyanophenoxy)phenoxy]phenyl]-3- methoxyacrylate, methyl (E)-2-[2-[(3-methyl-pyridin-2-yloxymethyl)phenyl]-3- methoxyacrylate, methyl (E)-2-[2-[6-(2-methyl-phenoxy)pyrimidin-4-yloxy]phenyl]-3- methoxyacrylate, methyl (E)-2-[2-(5-bromo-pyridin-2-yloxymethyl)phenyl]-3-methoxyacrylate, methyl (E)-2-[2-(3-(3-iodopyridin-2-yloxy)phenoxy)phenyl]-3-methoxyacrylate, methyl (E)-2- [2-[6-(2-chloropyridin-3-yloxy)pyrimidin-4-yloxy]phenyl]-3-methoxyac rylate, methyl (E),(E)-2- [2-(5,6-dimethylpyrazin-2-ylmethyloximinomethyl)phenyl]-3-methox yacrylate, methyl (E)-2- {2-[6-(6-methylpyridin-2-yloxy)pyrimidin-4-yloxy]phenyl}-3-methoxy-a crylate, methyl (E),(E)- 2-{ 2-(3-methoxyphenyl)methyloximinomethyl]-phenyl}-3-methoxyacrylate, methyl (E)-2-{2-(6- (2-azidophenoxy)-pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate, methyl (E),(E)-2-{2-[6- phenylpyrimidin-4-yl)-methyloximinomethyl]phenyl}-3-methox yacrylate, methyl (E),(E)-2-{2- [(4-chlorophenyl)-methyloximinomethyl]-phenyl}-3-methoxyacryl ate, methyl (E)-2-{2-[6-(2-n- propylphenoxy)-1 ,3,5-triazin-4-yloxy]phenyl}-3-methoxyacr ylate, methyl (E),(E)-2-{2-[(3- nitrophenyl)methyloximinomethyl]phenyl}-3-methoxyacrylate, 3-chloro-7-(2-aza-2,7,7- trimethyl-oct-3-en-5-ine), 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide, 3-iodo-2- propinyl alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenyl ethylcarbamate, 2,3,3-triiodoallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2- propinyl n-butylcarbamate, 3-iodo-2-propinyl n-hexylcarbamate, 3-iodo-2-propinyl cyclohexyl- carbamate, 3-iodo-2-propinyl phenylcarbamate; phenol derivatives, such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophene, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol, 5-hydroxy-2(5H)-furanone; 4,5-dichlorodithiazolinone, 4,5-benzodithiazolinone, 4,5- trimethylenedithiazolinone, 4,5-dichloro-(3H)-1 ,2-dithiol-3-one, 3,5-dimethyl-tetrahydro-1 ,3,5- thiadiazine-2-thione, N-(2-p-chlorobenzoylethyl)-hexaminium chloride, acibenzolar, acypetacs, alanycarb, albendazole, aldimorph, allicin, allyl alcohol, ametoctradin,
amisulbrom, amobam, ampropylfos, anilazine, asomate, aureofungin, azaconazole, azafendin, azithiram, azoxystrobin, barium polysulfide, benalaxyl, benalaxyl-M, benodanil, benomyl, benquinox, bentaluron, benthiavalicarb, benthiazole, benzalkonium chloride, benzamacril, benzamorf, benzohydroxamic acid, berberine, bethoxazin, biloxazol, binapacryl, biphenyl, bitertanol, bithionol, bixafen, blasticidin-S, boscalid, bromothalonil, bromuconazole, bupirimate, buthiobate, butylamine calcium polysulfide, captafol, captan, carbamorph, carbendazim, carbendazim chlorhydrate, carboxin, carpropamid, carvone, CGA41396, CGA41397, chinomethionate, chitosan, chlobenthiazone, chloraniformethan, chloranil, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlorozolinate, chlozolinate, climbazole, clotrimazole, clozylacon, copper containing compounds such as copper acetate, copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper oxyquinolate, copper silicate, copper sulphate, copper tallate, copper zinc chromate and Bordeaux mixture, cresol, cufraneb, cuprobam, cuprous oxide, cyazofamid,
cyclafuramid, cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazole, cyprodinil, dazomet, debacarb, decafentin, dehydroacetic acid, di-2-pyridyl disulphide 1 , 1 '- dioxide, dichlofluanid, diclomezine, dichlone, dicloran, dichlorophen, dichlozoline,
diclobutrazol, diclocymet, diethofencarb, difenoconazole, difenzoquat, diflumetorim, O, O-di- iso-propyl-S-benzyl thiophosphate, dimefluazole, dimetachlone, dimetconazole,
dimethomorph, dimethirimol, diniconazole, diniconazole-M, dinobuton, dinocap, dinocton, dinopenton, dinosulfon, dinoterbon, diphenylamine, dipyrithione, disulfiram, ditalimfos, dithianon, dithioether, dodecyl dimethyl ammonium chloride, dodemorph, dodicin, dodine, doguadine, drazoxolon, edifenphos, enestroburin, epoxiconazole, etaconazole, etem, ethaboxam, ethirimol, ethoxyquin, ethilicin, ethyl (Z)-N-benzyl-N ([methyl (methyl- thioethylideneamino- oxycarbonyl) amino] thio)^-alaninate, etridiazole, famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenitropan, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, flupicolide, fluopyram, fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutanil, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl, fuberidazole, furalaxyl, furametpyr, furcarbanil, furconazole, furfural, furmecyclox, furophanate, glyodin, griseofulvin, guazatine, halacrinate, hexa chlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexylthiofos, hydrargaphen, hydroxyisoxazole, hymexazole, imazalil, imazalil sulphate, imibenconazole, iminoctadine, iminoctadine triacetate, inezin, iodocarb, ipconazole, iprobenfos, iprodione, iprovalicarb, isopropanyl butyl carbamate, isoprothiolane, isopyrazam, isotianil, isovaledione, izopamfos, kasugamycin, kresoxim-methyl, LY186054, LY21 1795, LY248908, mancozeb, mandipropamid, maneb, mebenil, mecarbinzid, mefenoxam, mepanipyrim, mepronil, mercuric chloride, mercurous chloride, meptyldinocap, metalaxyl, metalaxyl-M, metam, metazoxolon, metconazole, methasulfocarb, methfuroxam, methyl bromide, methyl iodide, methyl isothiocyanate, metiram, metiram-zinc, metominostrobin, metrafenone, metsulfovax, milneb, moroxydine, myclobutanil, myclozolin, nabam, natamycin, neoasozin, nickel dimethyldithiocarbamate, nitrostyrene, nitrothal-iso- propyl, nuarimol, octhilinone, ofurace, organomercury compounds, orysastrobin, osthol, oxadixyl, oxasulfuron, oxine-copper, oxolinic acid, oxpoconazole, oxycarboxin, parinol, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, penthiopyrad, phenamacril, phenazin oxide, phosdiphen, phosetyl-AI, phosphorus acids, phthalide, picoxystrobin, piperalin,
polycarbamate, polyoxin D, polyoxrim, polyram, probenazole, prochloraz, procymidone, propamidine, propamocarb, propiconazole, propineb, propionic acid, proquinazid,
prothiocarb, prothioconazole, pyracarbolid, pyraclostrobin, pyrametrostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyridinitril, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, pyroxychlor, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinacetol, quinazamid, quinconazole, quinomethionate, quinoxyfen, quintozene, rabenzazole, santonin, sedaxane, silthiofam, simeconazole, sipconazole, sodium pentachlorophenate, solatenol, spiroxamine, streptomycin, sulphur, sultropen, tebuconazole, tebfloquin, tecloftalam, tecnazene, tecoram, tetraconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide, 2- (thiocyanomethylthio) benzothiazole, thiophanate-methyl, thioquinox, thiram, tiadinil, timibenconazole, tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triamiphos, triarimol, triazbutil, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumazole, triforine, triflumizole, triticonazole, uniconazole, urbacide, validamycin, valifenalate, vapam, vinclozolin, zarilamid, zineb, ziram, and zoxamide.
The compounds of the invention may also be used in combination with anthelmintic agents. Such anthelmintic agents include, compounds selected from the macrocyclic lactone class of compounds such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin derivatives as described in EP- 357460, EP-444964 and EP-594291 . Additional anthelmintic agents include
semisynthetic and biosynthetic avermectin/milbemycin derivatives such as those described in US-5015630, WO-9415944 and WO-9522552. Additional anthelmintic agents include the benzimidazoles such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, and other members of the class. Additional anthelmintic agents include imidazothiazoles and tetrahydropyrimidines such as tetramisole, levamisole, pyrantel pamoate, oxantel or morantel. Additional anthelmintic agents include flukicides, such as triclabendazole and clorsulon and the cestocides, such as praziquantel and epsiprantel.
The compounds of the invention may be used in combination with derivatives and analogues of the paraherquamide/marcfortine class of anthelmintic agents, as well as the antiparasitic oxazolines such as those disclosed in US-5478855, US- 4639771 and DE- 19520936.
The compounds of the invention may be used in combination with derivatives and analogues of the general class of dioxomorpholine antiparasitic agents as described in WO- 9615121 and also with anthelmintic active cyclic depsipeptides such as those described in WO-961 1945, WO-9319053, WO- 9325543, EP-626375, EP-382173, WO-9419334, EP- 382173, and EP-503538.
The compounds of the invention may be used in combination with other
ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like;
neonicotinoids such as imidacloprid and the like.
The compounds of the invention may be used in combination with terpene alkaloids, for example those described in International Patent Application Publication Numbers
W095/19363 or WO04/72086, particularly the compounds disclosed therein.
Other examples of such biologically active compounds that the compounds of the invention may be used in combination with include but are not restricted to the following:
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, methacriphos, methamidophos, methidathion, methyl- parathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, paraoxon, parathion, parathion-methyl, phenthoate, phosalone, phosfolan, phosphocarb, phosmet, phosphamidon, phorate, phoxim, pirimiphos, pirimiphos- methyl, profenofos, propaphos, proetamphos, prothiofos, pyraclofos,
pyridapenthion, quinalphos, sulprophos, temephos, terbufos, tebupirimfos, tetrachlorvinphos, thimeton, triazophos, trichlorfon, vamidothion.
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.
Pyrethroids: acrinathin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E) -(1 R)-cis- 2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, bifenthrin, beta - 5 cyfluthrin, cyfluthrin, a-cypermethrin, beta -cypermethrin, bioallethrin, bioallethrin((S)- cyclopentylisomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin, cythithrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, ethofenprox, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate (D isomer), imiprothrin, cyhalothrin, lambda-cyhalothrin, permethrin, phenothrin, prallethrin, pyrethrins (natural
10 products), resmethrin, tetramethrin, transfluthrin, theta-cypermethrin, silafluofen, t-fluvalinate, tefluthrin, tralomethrin, Zeta-cypermethrin.
Arthropod growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox,
15 etoxazole, chlorfentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide,
tebufenozide; c) juvenoids: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen.
Other antiparasitics: acequinocyl, amitraz, AKD-1022, ANS-1 18, azadirachtin, Bacillus thuringiensis, bensultap, bifenazate, binapacryl, bromopropylate, BTG-504, BTG-
20 505, 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,
25 neem guard, nidinorterfuran, nitenpyram, SD-35651 , WL-108477, pirydaryl, propargite,
protrifenbute, pymethrozine, pyridaben, pyrimidifen, NC-1 1 1 1 , R-195,RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601 , silafluofen, silomadine, spinosad, tebufenpyrad, tetradifon, tetranactin, thiacloprid, thiocyclam, thiamethoxam, tolfenpyrad, triazamate, triethoxyspinosyn, trinactin, verbutin, vertalec, YI-5301 .
30 Biological agents: Bacillus thuringiensis ssp aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, virus and fungi.
Bactericides: chlortetracycline, oxytetracycline, streptomycin.
Other biological agents: enrofloxacin, febantel, penethamate, moloxicam, cefalexin, kanamycin, pimobendan, clenbuterol, omeprazole, tiamulin, benazepril, pyriprole,
35 cefquinome, florfenicol, buserelin, cefovecin, tulathromycin, ceftiour, carprofen,
metaflumizone, praziquarantel, triclabendazole. The following mixtures of the compounds of formula I with active ingredients are preferred (the abbreviation "TX" means "one compound selected from the group consisting of the compounds described in A1 to A18 (above) of the present invention"):
an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX,
an acaricide selected from the group of substances consisting of 1 ,1 -bis(4-chloro- phenyl)-2-ethoxyethanol (lUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate (lUPAC/Chemical Abstracts name) (1059) + TX, 2-fluoro-/V-methyl-/V-1 -naphthylacetamide (lUPAC name) (1295) + TX, 4-chlorophenyl phenyl sulfone (lUPAC name) (981 ) + TX, abamectin (1 ) + TX, acequinocyl (3) + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, alpha-cypermethrin (202) + TX, amidithion (870) + TX, amidoflumet [CCN] + TX, amidothioate (872) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, aramite (881 ) + TX, arsenous oxide (882) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azobenzene (lUPAC name) (888) + TX, azocyclotin (46) + TX, azothoate (889) + TX, benomyl (62) + TX, benoxafos (alternative name) [CCN] + TX, benzoximate (71 ) + TX, benzyl benzoate (lUPAC name) [CCN] + TX, bifenazate (74) + TX, bifenthrin (76) + TX, binapacryl (907) + TX, brofenvalerate (alternative name) + TX, bromo- cyclen (918) + TX, bromophos (920) + TX, bromophos-ethyl (921 ) + TX, bromopropylate (94) + TX, buprofezin (99) + TX, butocarboxim (103) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, calcium polysulfide (lUPAC name) (1 1 1 ) + TX, camphechlor (941 ) + TX, carbanolate (943) + TX, carbaryl (1 15) + TX, carbofuran (1 18) + TX, carbophenothion (947) + TX, CGA 50'439 (development code) (125) + TX, chino- methionat (126) + TX, chlorbenside (959) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorfenapyr (130) + TX, chlorfenethol (968) + TX, chlorfenson (970) + TX, chlorfensulfide (971 ) + TX, chlorfenvinphos (131 ) + TX, chlorobenzilate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, clofentezine (158) + TX, closantel (alternative name) [CCN] + TX, coumaphos (174) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos (1010) + TX, cufraneb (1013) + TX, cyanthoate (1020) + TX, cyflumetofen (CAS Reg. No.: 400882-07-7) + TX, cyhalothrin (196) + TX, cyhexatin (199) + TX, cypermethrin (201 ) + TX, DCPM (1032) + TX, DDT (219) + TX, demephion (1037) + TX, demephion-0 (1037) + TX, demephion-S (1037) + TX, demeton (1038) + TX, demeton- methyl (224) + TX, demeton-0 (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-S-methyl (224) + TX, demeton-S-methylsulfon (1039) + TX, diafen- thiuron (226) + TX, dialifos (1042) + TX, diazinon (227) + TX, dichlofluanid (230) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicofol (242) + TX, dicrotophos (243) + TX, dienochlor (1071 ) + TX, dimefox (1081 ) + TX, dimethoate (262) + TX, dinactin (alternative name) (653) + TX, dinex (1089) + TX, dinex-diclexine (1089) + TX, dinobuton (269) + TX, dinocap (270) + TX, dinocap-4 [CCN] + TX, dinocap-6 [CCN] + TX, dinocton (1090) + TX, dinopenton (1092) + TX, dinosulfon (1097) + TX, dinoterbon (1098) + TX, dioxathion (1 102) + TX, diphenyl sulfone (lUPAC name) (1 103) + TX, disulfiram (alternative name) [CCN] + TX, disulfoton (278) + TX, DNOC (282) + TX, dofenapyn (1 1 13) + TX, doramectin (alternative name) [CCN] + TX, endosulfan (294) + TX, endothion (1 121 ) + TX, EPN (297) + TX, eprinomectin (alternative name) [CCN] + TX, ethion (309) + TX, ethoate- methyl (1 134) + TX, etoxazole (320) + TX, etrimfos (1 142) + TX, fenazaflor (1 147) + TX, fenazaquin (328) + TX, fenbutatin oxide (330) + TX, fenothiocarb (337) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fenpyroximate (345) + TX, fenson (1 157) + TX, fentrifanil (1 161 ) + TX, fenvalerate (349) + TX, fipronil (354) + TX, fluacrypyrim (360) + TX, fluazuron (1 166) + TX, flubenzimine (1 167) + TX, flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1 169) + TX, flufenoxuron (370) + TX, flumethrin (372) + TX,
fluorbenside (1 174) + TX, fluvalinate (1 184) + TX, FMC 1 137 (development code) (1 185) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1 192) + TX, formparanate (1 193) + TX, gamma-HCH (430) + TX, glyodin (1205) + TX, halfenprox (424) + TX, heptenophos (432) + TX, hexadecyl cyclopropanecarboxylate (lUPAC/Chemical
Abstracts name) (1216) + TX, hexythiazox (441 ) + TX, iodomethane (lUPAC name) (542) + TX, isocarbophos (alternative name) (473) + TX, isopropyl O-
(methoxyaminothiophosphoryl)salicylate (lUPAC name) (473) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, lindane (430) + TX, lufenuron (490) + TX, malathion (492) + TX, malonoben (1254) + TX, mecarbam (502) + TX, mephosfolan (1261 ) + TX, mesulfen (alternative name) [CCN] + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methidathion (529) + TX, methiocarb (530) + TX, methomyl (531 ) + TX, methyl bromide (537) + TX, metolcarb (550) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, monocrotophos (561 ) + TX,
morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naled (567) + TX, NC- 184 (compound code) + TX, NC-512 (compound code) + TX, nifluridide (1309) + TX, nikkomycins (alternative name) [CCN] + TX, nitrilacarb (1313) + TX, nitrilacarb 1 :1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydeprofos (1324) + TX,
oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, parathion (615) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, phenkapton (1330) + TX, phenthoate (631 ) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosphamidon (639) + TX, phoxim (642) + TX, pirimiphos-methyl (652) + TX, polychloroterpenes (traditional name) (1347) + TX, polynactins (alternative name) (653) + TX, proclonol (1350) + TX, profenofos (662) + TX, promacyl (1354) + TX, propargite (671 ) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothoate (1362) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridaphenthion (701 ) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, quinalphos (71 1 ) + TX, quintiofos (1381 ) + TX, R-1492 (development code) (1382) + TX, RA- 17 (development code) (1383) + TX, rotenone (722) + TX, schradan (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, sophamide (1402) + TX, spirodiclofen (738) + TX, spiromesifen (739) + TX, SSI- 121 (development code) (1404) + TX, sulfiram (alternative name) [CCN] + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulfur (754) + TX, SZI-121 (development code) (757) + TX, tau-fluvalinate (398) + TX, tebufenpyrad (763) + TX, TEPP (1417) + TX, terbam (alternative name) + TX, tetrachlorvinphos (777) + TX, tetradifon (786) + TX, tetranactin (alternative name) (653) + TX, tetrasul (1425) + TX, thiafenox (alternative name) + TX, thiocarboxime (1431 ) + TX, thiofanox (800) + TX, thiometon (801 ) + TX, thioquinox (1436) + TX, thuringiensin (alternative name) [CCN] + TX, triamiphos (1441 ) + TX, triarathene (1443) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, trifenofos (1455) + TX, trinactin (alternative name) (653) + TX, vamidothion (847) + TX, vaniliprole [CCN] and YI-5302 (compound code) + TX,
an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (lUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (lUPAC name) (347) and triphenyltin hydroxide (lUPAC name) (347) + TX,
an anthelmintic selected from the group of substances consisting of abamectin (1 ) + TX, crufomate (101 1 ) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291 ) + TX, emamectin benzoate (291 ) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,
an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1 122) + TX, fenthion (346) + TX, pyridin-4-amine (lUPAC name) (23) and strychnine (745) + TX,
a bactericide selected from the group of substances consisting of 1 -hydroxy-1 /-/- pyridine-2-thione (lUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (lUPAC name) (170) + TX, copper hydroxide (lUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1 105) + TX, dodicin (1 1 12) + TX, fenaminosulf (1 144) + TX, formaldehyde (404) + TX, hydrargaphen (alternative name) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (lUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (61 1 ) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, tecloftalam (766) + TX, and thiomersal (alternative name) [CCN] + TX,
a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX, Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis (alternative name) (33) + TX, Aphidius colemani (alternative name) (34) + TX, Aphidoletes aphidimyza (alternative name) (35) + TX, Autographa californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide (scientific name) (49) + TX, Bacillus thuringiensis Berliner (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51 ) + TX, Bacillus thuringiensis subsp.
israelensis (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. japonensis (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. tenebrionis (scientific name) (51 ) + TX, Beauveria bassiana (alternative name) (53) + TX, Beauveria brongniartii (alternative name) (54) + TX, Chrysoperla carnea (alternative name) (151 ) + TX, Cryptolaemus montrouzieri (alternative name) (178) + TX, Cydia pomonella GV (alternative name) (191 ) + TX, Dacnusa sibirica (alternative name) (212) + TX, Diglyphus isaea (alternative name) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus (alternative name) (300) + TX, Helicoverpa zea NPV (alternative name) (431 ) + TX, Heterorhabditis bacteriophora and H. megidis
(alternative name) (433) + TX, Hippodamia convergens (alternative name) (442) + TX, Leptomastix dactylopii (alternative name) (488) + TX, Macrolophus caliginosus (alternative name) (491 ) + TX, Mamestra brassicae NPV (alternative name) (494) + TX, Metaphycus helvolus (alternative name) (522) + TX, Metarhizium anisopliae var. acridum (scientific name) (523) + TX, Metarhizium anisopliae var. anisopliae (scientific name) (523) + TX, Neodiprion sertifer NPV and N. lecontei NPV (alternative name) (575) + TX, Orius spp. (alternative name) (596) + TX, Paecilomyces fumosoroseus (alternative name) (613) + TX, Phytoseiulus persimilis (alternative name) (644) + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741 ) + TX, Steinernema bibionis (alternative name) (742) + TX, Steinernema carpocapsae (alternative name) (742) + TX, Steinernema feltiae (alternative name) (742) + TX, Steinernema glaseri (alternative name) (742) + TX, Steinernema riobrave (alternative name) (742) + TX, Steinernema riobravis (alternative name) (742) + TX, Steinernema scapterisci (alternative name) (742) + TX, Steinernema spp. (alternative name) (742) + TX, Trichogramma spp. (alternative name) (826) + TX, Typhlodromus occidentalis (alternative name) (844) and Verticillium lecanii (alternative name) (848) + TX,
a soil sterilant selected from the group of substances consisting of iodomethane (lUPAC name) (542) and methyl bromide (537) + TX,
a chemosterilant selected from the group of substances consisting of apholate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholate [CCN] + TX, morzid [CCN] + TX, penfluron (alternative name) [CCN] + TX, tepa [CCN] + TX, thiohempa (alternative name) [CCN] + TX, thiotepa (alternative name) [CCN] + TX, tretamine
(alternative name) [CCN] and uredepa (alternative name) [CCN] + TX,
an insect pheromone selected from the group of substances consisting of (£)-dec-5- en-1 -yl acetate with (£)-dec-5-en-1 -ol (lUPAC name) (222) + TX, (£)-tridec-4-en-1 -yl acetate (lUPAC name) (829) + TX, (£)-6-methylhept-2-en-4-ol (lUPAC name) (541 ) + TX, (£,Z)- tetradeca-4,10-dien-1 -yl acetate (lUPAC name) (779) + TX, (Z)-dodec-7-en-1 -yl acetate (lUPAC name) (285) + TX, (Z)-hexadec-l 1 -enal (lUPAC name) (436) + TX, (Z)-hexadec-l 1 - en-1 -yl acetate (lUPAC name) (437) + TX, (Z)-hexadec-13-en-1 1 -yn-1 -yl acetate (lUPAC name) (438) + TX, (Z)-icos-13-en-10-one (lUPAC name) (448) + TX, (Z)-tetradec-7-en-1 -al (lUPAC name) (782) + TX, (Z)-tetradec-9-en-1 -ol (lUPAC name) (783) + TX, (Z)-tetradec-9- en-1 -yl acetate (lUPAC name) (784) + TX, (7£,9Z)-dodeca-7,9-dien-1 -yl acetate (lUPAC name) (283) + TX, (9Z,1 1 £)-tetradeca-9,1 1 -dien-1-yl acetate (lUPAC name) (780) + TX, (9Z, 12£)-tetradeca-9,12-dien-1 -yl acetate (lUPAC name) (781 ) + TX, 14-methyloctadec-1 - ene (lUPAC name) (545) + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one (lUPAC name) (544) + TX, alpha-multistriatin (alternative name) [CCN] + TX, brevicomin (alternative name) [CCN] + TX, codlelure (alternative name) [CCN] + TX, codlemone (alternative name) (167) + TX, cuelure (alternative name) (179) + TX, disparlure (277) + TX, dodec-8-en-1 -yl acetate (lUPAC name) (286) + TX, dodec-9-en-1 -yl acetate (lUPAC name) (287) + TX, dodeca-8 + TX, 10-dien-1 -yl acetate (lUPAC name) (284) + TX, dominicalure (alternative name) [CCN] + TX, ethyl 4-methyloctanoate (lUPAC name) (317) + TX, eugenol (alternative name) [CCN] + TX, frontalin (alternative name) [CCN] + TX, gossyplure (alternative name) (420) + TX, grandlure (421 ) + TX, grandlure I (alternative name) (421 ) + TX, grandlure II (alternative name) (421 ) + TX, grandlure III (alternative name) (421 ) + TX, grandlure IV (alternative name) (421 ) + TX, hexalure [CCN] + TX, ipsdienol (alternative name) [CCN] + TX, ipsenol (alternative name) [CCN] + TX, japonilure (alternative name) (481 ) + TX, lineatin (alternative name) [CCN] + TX, litlure (alternative name) [CCN] + TX, looplure (alternative name) [CCN] + TX, medlure [CCN] + TX, megatomoic acid (alternative name) [CCN] + TX, methyl eugenol (alternative name) (540) + TX, muscalure (563) + TX, octadeca-2,13-dien-1 - yl acetate (lUPAC name) (588) + TX, octadeca-3,13-dien-1 -yl acetate (lUPAC name) (589) + TX, orfralure (alternative name) [CCN] + TX, oryctalure (alternative name) (317) + TX, ostramone (alternative name) [CCN] + TX, siglure [CCN] + TX, sordidin (alternative name) (736) + TX, sulcatol (alternative name) [CCN] + TX, tetradec-1 1 -en-1 -yl acetate (lUPAC name) (785) + TX, trimedlure (839) + TX, trimedlure A (alternative name) (839) + TX, trimedlure B-i (alternative name) (839) + TX, trimedlure B2 (alternative name) (839) + TX, trimedlure C (alternative name) (839) and trunc-call (alternative name) [CCN] + TX,
an insect repellent selected from the group of substances consisting of 2-(octylthio)- ethanol (lUPAC name) (591 ) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (lUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (lUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1 137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,
an insecticide selected from the group of substances consisting of 1 -dichloro-1 - nitroethane (lUPAC/Chemical Abstracts name) (1058) + TX, 1 ,1 -dichloro-2,2-bis(4- ethylphenyl)ethane (lUPAC name) (1056), + TX, 1 ,2-dichloropropane (lUPAC/Chemical Abstracts name) (1062) + TX, 1 ,2-dichloropropane with 1 ,3-dichloropropene (lUPAC name) (1063) + TX, 1 -bromo-2-chloroethane (lUPAC/Chemical Abstracts name) (916) + TX, 2,2,2- trichloro-1 -(3,4-dichlorophenyl)ethyl acetate (lUPAC name) (1451 ) + TX, 2,2-dichlorovinyl 2- ethylsulfinylethyl methyl phosphate (lUPAC name) (1066) + TX, 2-(1 ,3-dithiolan-2-yl)phenyl dimethylcarbamate (lUPAC/ Chemical Abstracts name) (1 109) + TX, 2-(2-butoxyethoxy)ethyl thiocyanate (lUPAC/Chemical Abstracts name) (935) + TX, 2-(4,5-dimethyl-1 ,3-dioxolan-2- yl)phenyl methylcarbamate (lUPAC/ Chemical Abstracts name) (1084) + TX, 2-(4-chloro-3,5- xylyloxy)ethanol (lUPAC name) (986) + TX, 2-chlorovinyl diethyl phosphate (lUPAC name) (984) + TX, 2-imidazolidone (lUPAC name) (1225) + TX, 2-isovalerylindan-1 ,3-dione (lUPAC name) (1246) + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate (lUPAC name) (1284) + TX, 2-thiocyanatoethyl laurate (lUPAC name) (1433) + TX, 3-bromo-1 -chloroprop-1 - ene (lUPAC name) (917) + TX, 3-methyl-1 -phenylpyrazol-5-yl dimethylcarbamate (lUPAC name) (1283) + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate (lUPAC name) (1285) + TX, 5,5-dimethyl-3-oxocyclohex-1 -enyl dimethylcarbamate (lUPAC name) (1085) + TX, abamectin (1 ) + TX, acephate (2) + TX, acetamiprid (4) + TX, acethion (alternative name) [CCN] + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, acrylonitrile (lUPAC name) (861 ) + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, aldrin (864) + TX, allethrin (17) + TX, allosamidin (alternative name) [CCN] + TX, allyxycarb (866) + TX, alpha-cypermethrin (202) + TX, alpha-ecdysone (alternative name) [CCN] + TX, aluminium phosphide (640) + TX, amidithion (870) + TX, amidothioate (872) + TX, aminocarb (873) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, anabasine (877) + TX, athidathion (883) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azadirachtin (alternative name) (41 ) + TX, azamethiphos (42) + TX, azinphos- ethyl (44) + TX, azinphos-methyl (45) + TX, azothoate (889) + TX, Bacillus thuringiensis delta endotoxins (alternative name) (52) + TX, barium hexafluorosilicate (alternative name) [CCN] + TX, barium polysulfide (lUPAC/Chemical Abstracts name) (892) + TX, barthrin [CCN] + TX, Bayer 22/190 (development code) (893) + TX, Bayer 22408 (development code) (894) + TX, bendiocarb (58) + TX, benfuracarb (60) + TX, bensultap (66) + TX, beta-cyfluthrin (194) + TX, beta-cypermethrin (203) + TX, bifenthrin (76) + TX, bioallethrin (78) + TX, bioallethrin S- cyclopentenyl isomer (alternative name) (79) + TX, bioethanomethrin [CCN] + TX, biopermethrin (908) + TX, bioresmethrin (80) + TX, bis(2-chloroethyl) ether (lUPAC name) (909) + TX, bistrifluron (83) + TX, borax (86) + TX, brofenvalerate (alternative name) + TX, bromfenvinfos (914) + TX, bromocyclen (918) + TX, bromo-DDT (alternative name) [CCN] + TX, bromophos (920) + TX, bromophos-ethyl (921 ) + TX, bufencarb (924) + TX, buprofezin (99) + TX, butacarb (926) + TX, butathiofos (927) + TX, butocarboxim (103) + TX, butonate (932) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, calcium arsenate [CCN] + TX, calcium cyanide (444) + TX, calcium polysulfide (lUPAC name) (1 1 1 ) + TX, camphechlor (941 ) + TX, carbanolate (943) + TX, carbaryl (1 15) + TX, carbofuran (1 18) + TX, carbon disulfide (lUPAC/Chemical Abstracts name) (945) + TX, carbon tetrachloride (lUPAC name) (946) + TX, carbophenothion (947) + TX, carbosulfan (1 19) + TX, cartap (123) + TX, cartap hydrochloride (123) + TX, cevadine (alternative name) (725) + TX, chlorbicyclen (960) + TX, chlordane (128) + TX, chlordecone (963) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorethoxyfos (129) + TX, chlorfenapyr (130) + TX, chlorfenvinphos (131 ) + TX, chlorfluazuron (132) + TX, chlormephos (136) + TX, chloroform [CCN] + TX, chloropicrin (141 ) + TX, chlorphoxim (989) + TX, chlorprazophos (990) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, chromafenozide (150) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, cis-resmethrin (alternative name) + TX, cismethrin (80) + TX, clocythrin (alternative name) + TX, cloethocarb (999) + TX, closantel (alternative name) [CCN] + TX, clothianidin (165) + TX, copper acetoarsenite [CCN] + TX, copper arsenate [CCN] + TX, copper oleate [CCN] + TX, coumaphos (174) + TX, coumithoate (1006) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos (1010) + TX, crufomate (101 1 ) + TX, cryolite (alternative name) (177) + TX, CS 708 (development code) (1012) + TX, cyanofenphos (1019) + TX, cyanophos (184) + TX, cyanthoate (1020) + TX, cyclethrin [CCN] + TX, cycloprothrin (188) + TX, cyfluthrin (193) + TX, cyhalothrin (196) + TX, cypermethrin (201 ) + TX, cyphenothrin (206) + TX, cyromazine (209) + TX, cythioate (alternative name) [CCN] + TX, d-limonene (alternative name) [CCN] + TX, cZ-tetramethrin (alternative name) (788) + TX, DAEP (1031 ) + TX, dazomet (216) + TX, DDT (219) + TX, decarbofuran (1034) + TX, deltamethrin (223) + TX, demephion (1037) + TX, demephion-0 (1037) + TX,
demephion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-O (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-S-methyl (224) + TX, demeton-S-methylsulphon (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diamidafos (1044) + TX, diazinon (227) + TX, dicapthon (1050) + TX, dichlofenthion (1051 ) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicresyl (alternative name) [CCN] + TX, dicrotophos (243) + TX, dicyclanil (244) + TX, dieldrin (1070) + TX, diethyl 5-methylpyrazol-3-yl phosphate (lUPAC name) (1076) + TX, diflubenzuron (250) + TX, dilor (alternative name) [CCN] + TX, dimefluthrin [CCN] + TX, dimefox (1081 ) + TX, dimetan (1085) + TX, dimethoate (262) + TX, dimethrin (1083) + TX, dimethylvinphos (265) + TX, dimetilan (1086) + TX, dinex (1089) + TX, dinex-diclexine (1089) + TX, dinoprop (1093) + TX, dinosam (1094) + TX, dinoseb (1095) + TX, dinotefuran (271 ) + TX, diofenolan (1099) + TX, dioxabenzofos (1 100) + TX, dioxacarb (1 101 ) + TX, dioxathion (1 102) + TX, disulfoton (278) + TX, dithicrofos (1 108) + TX, DNOC (282) + TX, doramectin (alternative name) [CCN] + TX, DSP (1 1 15) + TX, ecdysterone (alternative name) [CCN] + TX, El 1642 (development code) (1 1 18) + TX, emamectin (291 ) + TX, emamectin benzoate (291 ) + TX, EMPC (1 120) + TX, empenthrin (292) + TX, endosulfan (294) + TX, endothion (1 121 ) + TX, endrin (1 122) + TX, EPBP (1 123) + TX, EPN (297) + TX, epofenonane (1 124) + TX, eprinomectin (alternative name) [CCN] + TX, esfenvalerate (302) + TX, etaphos (alternative name) [CCN] + TX, ethiofencarb (308) + TX, ethion (309) + TX, ethiprole (310) + TX, ethoate-methyl (1 134) + TX, ethoprophos (312) + TX, ethyl formate (lUPAC name) [CCN] + TX, ethyl-DDD
(alternative name) (1056) + TX, ethylene dibromide (316) + TX, ethylene dichloride (chemical name) (1 136) + TX, ethylene oxide [CCN] + TX, etofenprox (319) + TX, etrimfos (1 142) + TX, EXD (1 143) + TX, famphur (323) + TX, fenamiphos (326) + TX, fenazaflor (1 147) + TX, fenchlorphos (1 148) + TX, fenethacarb (1 149) + TX, fenfluthrin (1 150) + TX, fenitrothion (335) + TX, fenobucarb (336) + TX, fenoxacrim (1 153) + TX, fenoxycarb (340) + TX, fenpirithrin (1 155) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fensulfothion (1 158) + TX, fenthion (346) + TX, fenthion-ethyl [CCN] + TX, fenvalerate (349) + TX, fipronil (354) + TX, flonicamid (358) + TX, flubendiamide (CAS. Reg. No.: 272451 -65- 7) + TX, flucofuron (1 168) + TX, flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1 169) + TX, flufenerim [CCN] + TX, flufenoxuron (370) + TX, flufenprox (1 171 ) + TX, flumethrin (372) + TX, fluvalinate (1 184) + TX, FMC 1 137 (development code) (1 185) + TX, fonofos (1 191 ) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1 192) + TX, formparanate (1 193) + TX, fosmethilan (1 194) + TX, fospirate (1 195) + TX, fosthiazate (408) + TX, fosthietan (1 196) + TX, furathiocarb (412) + TX, furethrin (1200) + TX, gamma-cyhalothrin (197) + TX, gamma-HCH (430) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, GY-81 (development code) (423) + TX, halfenprox (424) + TX, halofenozide (425) + TX, HCH (430) + TX, HEOD (1070) + TX, heptachlor (121 1 ) + TX, heptenophos (432) + TX, heterophos [CCN] + TX, hexaflumuron (439) + TX, HHDN (864) + TX, hydramethylnon (443) + TX, hydrogen cyanide (444) + TX, hydroprene (445) + TX, hyquincarb (1223) + TX, imidacloprid (458) + TX, imiprothrin (460) + TX, indoxacarb (465) + TX, iodomethane (lUPAC name) (542) + TX, IPSP (1229) + TX, isazofos (1231 ) + TX, isobenzan (1232) + TX, isocarbophos (alternative name) (473) + TX, isodrin (1235) + TX, isofenphos (1236) + TX, isolane (1237) + TX, isoprocarb (472) + TX, isopropyl 0-(methoxy- aminothiophosphoryl)salicylate (lUPAC name) (473) + TX, isoprothiolane (474) + TX, isothioate (1244) + TX, isoxathion (480) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, juvenile hormone I (alternative name) [CCN] + TX, juvenile hormone II (alternative name) [CCN] + TX, juvenile hormone III (alternative name) [CCN] + TX, kelevan (1249) + TX, kinoprene (484) + TX, lambda-cyhalothrin (198) + TX, lead arsenate [CCN] + TX, lepimectin (CCN) + TX, leptophos (1250) + TX, lindane (430) + TX, lirimfos (1251 ) + TX, lufenuron (490) + TX, lythidathion (1253) + TX, m-cumenyl methylcarbamate (lUPAC name) (1014) + TX, magnesium phosphide (lUPAC name) (640) + TX, malathion (492) + TX, malonoben (1254) + TX, mazidox (1255) + TX, mecarbam (502) + TX, mecarphon (1258) + TX, menazon (1260) + TX, mephosfolan (1261 ) + TX, mercurous chloride (513) + TX, mesulfenfos (1263) + TX, metaflumizone (CCN) + TX, metam (519) + TX, metam-potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methanesulfonyl fluoride (lUPAC/Chemical Abstracts name) (1268) + TX, methidathion (529) + TX, methiocarb (530) + TX, methocrotophos (1273) + TX, methomyl (531 ) + TX, methoprene (532) + TX, methoquin-butyl (1276) + TX, methothrin (alternative name) (533) + TX, methoxychlor (534) + TX, methoxyfenozide (535) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, methylchloroform (alternative name) [CCN] + TX, methylene chloride [CCN] + TX, metofluthrin [CCN] + TX, metolcarb (550) + TX,
metoxadiazone (1288) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, mirex (1294) + TX, monocrotophos (561 ) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naftalofos (alternative name) [CCN] + TX, naled (567) + TX, naphthalene (lUPAC/Chemical Abstracts name) (1303) + TX, NC-170 (development code) (1306) + TX, NC-184 (compound code) + TX, nicotine (578) + TX, nicotine sulfate (578) + TX, nifluridide (1309) + TX, nitenpyram (579) + TX, nithiazine (131 1 ) + TX, nitrilacarb (1313) + TX, nitrilacarb 1 :1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI- 0250 (compound code) + TX, nornicotine (traditional name) (1319) + TX, novaluron (585) + TX, noviflumuron (586) + TX, 0-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate (lUPAC name) (1057) + TX, 0,0-diethyl 0-4-methyl-2-oxo-2H-chromen-7-yl
phosphorothioate (lUPAC name) (1074) + TX, Ο,Ο-diethyl 0-6-methyl-2-propylpyrimidin-4-yl phosphorothioate (lUPAC name) (1075) + TX, O, Ο,Ο', O'-tetrapropyl dithiopyrophosphate (lUPAC name) (1424) + TX, oleic acid (lUPAC name) (593) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydemeton-methyl (609) + TX, oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, para-dichlorobenzene [CCN] + TX, parathion (615) + TX, parathion-methyl (616) + TX, penfluron (alternative name) [CCN] + TX, pentachlorophenol (623) + TX, pentachlorophenyl laurate (lUPAC name) (623) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, PH 60-38 (development code) (1328) + TX, phenkapton (1330) + TX, phenothrin (630) + TX, phenthoate (631 ) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosnichlor (1339) + TX, phosphamidon (639) + TX, phosphine (lUPAC name) (640) + TX, phoxim (642) + TX, phoxim-methyl (1340) + TX, pirimetaphos (1344) + TX, pirimicarb (651 ) + TX, pirimiphos- ethyl (1345) + TX, pirimiphos-methyl (652) + TX, polychlorodicyclopentadiene isomers (lUPAC name) (1346) + TX, polychloroterpenes (traditional name) (1347) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate [CCN] + TX, prallethrin (655) + TX, precocene I (alternative name) [CCN] + TX, precocene II (alternative name) [CCN] + TX, precocene III (alternative name) [CCN] + TX, primidophos (1349) + TX, profenofos (662) + TX, profluthrin [CCN] + TX, promacyl (1354) + TX, promecarb (1355) + TX, propaphos (1356) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothiofos (686) + TX, prothoate (1362) + TX, protrifenbute [CCN] + TX, pymetrozine (688) + TX, pyraclofos (689) + TX, pyrazophos (693) + TX, pyresmethrin (1367) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridalyl (700) + TX, pyridaphenthion (701 ) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, pyriproxyfen (708) + TX, quassia (alternative name) [CCN] + TX, quinalphos (71 1 ) + TX, quinalphos- methyl (1376) + TX, quinothion (1380) + TX, quintiofos (1381 ) + TX, R-1492 (development code) (1382) + TX, rafoxanide (alternative name) [CCN] + TX, resmethrin (719) + TX, rotenone (722) + TX, RU 15525 (development code) (723) + TX, RU 25475 (development code) (1386) + TX, ryania (alternative name) (1387) + TX, ryanodine (traditional name) (1387) + TX, sabadilla (alternative name) (725) + TX, schradan (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, SI-0205 (compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, silafluofen (728) + TX, SN 72129 (development code) (1397) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoride (lUPAC/Chemical Abstracts name) (1399) + TX, sodium hexafluorosilicate (1400) + TX, sodium
pentachlorophenoxide (623) + TX, sodium selenate (lUPAC name) (1401 ) + TX, sodium thiocyanate [CCN] + TX, sophamide (1402) + TX, spinosad (737) + TX, spiromesifen (739) + TX, spirotetrmat (CCN) + TX, sulcofuron (746) + TX, sulcofuron-sodium (746) + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulfuryl fluoride (756) + TX, sulprofos (1408) + TX, tar oils (alternative name) (758) + TX, tau-fluvalinate (398) + TX, tazimcarb (1412) + TX, TDE (1414) + TX, tebufenozide (762) + TX, tebufenpyrad (763) + TX, tebupirimfos (764) + TX, teflubenzuron (768) + TX, tefluthrin (769) + TX, temephos (770) + TX, TEPP (1417) + TX, terallethrin (1418) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachloroethane [CCN] + TX, tetrachlorvinphos (777) + TX, tetramethrin (787) + TX, theta- cypermethrin (204) + TX, thiacloprid (791 ) + TX, thiafenox (alternative name) + TX, thiamethoxam (792) + TX, thicrofos (1428) + TX, thiocarboxime (1431 ) + TX, thiocyclam (798) + TX, thiocyclam hydrogen oxalate (798) + TX, thiodicarb (799) + TX, thiofanox (800) + TX, thiometon (801 ) + TX, thionazin (1434) + TX, thiosultap (803) + TX, thiosultap-sodium (803) + TX, thuringiensin (alternative name) [CCN] + TX, tolfenpyrad (809) + TX, tralomethrin (812) + TX, transfluthrin (813) + TX, transpermethrin (1440) + TX, triamiphos (1441 ) + TX, triazamate (818) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, trichlormetaphos-3 (alternative name) [CCN] + TX, trichloronat (1452) + TX, trifenofos (1455) + TX, triflumuron (835) + TX, trimethacarb (840) + TX, triprene (1459) + TX, vamidothion (847) + TX, vaniliprole [CCN] + TX, veratridine (alternative name) (725) + TX, veratrine (alternative name) (725) + TX, XMC (853) + TX, xylylcarb (854) + TX, YI-5302 (compound code) + TX, zeta-cypermethrin (205) + TX, zetamethrin (alternative name) + TX, zinc phosphide (640) + TX, zolaprofos (1469) and ZXI 8901 (development code) (858) + TX, cyantraniliprole [736994-63-19 + TX, chlorantraniliprole [500008-45-7] + TX, cyenopyrafen [560121 -52-0] + TX, cyflumetofen [400882-07-7] + TX, pyrifluquinazon [337458-27-2] + TX, spinetoram [187166-40-1 + 187166-15-0] + TX, spirotetramat [203313-25-1 ] + TX, sulfoxaflor [946578-00-3] + TX, flufiprole [704886-18-0] + TX, meperfluthrin [915288-13-0] + TX, tetramethylfluthrin [84937-88-2] + TX, triflumezopyrim (disclosed in WO 2012/0921 15) + TX, a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (lUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (lUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX,
pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, trifenmorph (1454) + TX, trimethacarb (840) + TX, triphenyltin acetate (lUPAC name) (347) and triphenyltin hydroxide (lUPAC name) (347) + TX, pyriprole [394730-71 -3] + TX,
a nematicide selected from the group of substances consisting of AKD-3088
(compound code) + TX, 1 ,2-dibromo-3-chloropropane (lUPAC/Chemical Abstracts name) (1045) + TX, 1 ,2-dichloropropane (lUPAC/ Chemical Abstracts name) (1062) + TX, 1 ,2- dichloropropane with 1 ,3-dichloropropene (lUPAC name) (1063) + TX, 1 ,3-dichloropropene (233) + TX, 3,4-dichlorotetrahydrothiophene 1 ,1 -dioxide (lUPAC/Chemical Abstracts name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (lUPAC name) (980) + TX, 5-methyl-6- thioxo-1 ,3,5-thiadiazinan-3-ylacetic acid (lUPAC name) (1286) + TX, 6- isopentenylaminopurine (alternative name) (210) + TX, abamectin (1 ) + TX, acetoprole
[CCN] + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, AZ 60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben
(alternative name) + TX, cadusafos (109) + TX, carbofuran (1 18) + TX, carbon disulfide (945) + TX, carbosulfan (1 19) + TX, chloropicrin (141 ) + TX, chlorpyrifos (145) + TX, cloethocarb (999) + TX, cytokinins (alternative name) (210) + TX, dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidafos (1044) + TX, dichlofenthion (1051 ) + TX, dicliphos
(alternative name) + TX, dimethoate (262) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291 ) + TX, emamectin benzoate (291 ) + TX, eprinomectin (alternative name) [CCN] + TX, ethoprophos (312) + TX, ethylene dibromide (316) + TX, fenamiphos (326) + TX, fenpyrad (alternative name) + TX, fensulfothion (1 158) + TX, fosthiazate (408) + TX, fosthietan (1 196) + TX, furfural (alternative name) [CCN] + TX, GY-81 (development code) (423) + TX, heterophos [CCN] + TX, iodomethane (lUPAC name) (542) + TX, isamidofos (1230) + TX, isazofos (1231 ) + TX, ivermectin (alternative name) [CCN] + TX, kinetin
(alternative name) (210) + TX, mecarphon (1258) + TX, metam (519) + TX, metam- potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, Myrothecium verrucaria composition (alternative name) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidon (639) + TX, phosphocarb [CCN] + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachlorothiophene (lUPAC/ Chemical Abstracts name) (1422) + TX, thiafenox (alternative name) + TX, thionazin (1434) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, xylenols [CCN] + TX, YI-5302 (compound code) and zeatin (alternative name) (210) + TX, fluensulfone [318290-98-1] + TX,
a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX, a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX,
a rodenticide selected from the group of substances consisting of 2-isovalerylindan- 1 ,3-dione (lUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891 ) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91 ) + TX, bromethalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorophacinone (140) + TX, cholecalciferol (alternative name) (850) + TX, coumachlor (1004) + TX, coumafuryl (1005) + TX, coumatetralyl (175) + TX, crimidine (1009) + TX, difenacoum (246) + TX, difethialone (249) + TX, diphacinone (273) + TX, ergocalciferol (301 ) + TX, flocoumafen (357) + TX, fluoroacetamide (379) + TX, flupropadine (1 183) + TX, flupropadine hydrochloride (1 183) + TX, gamma-HCH (430) + TX, HCH (430) + TX, hydrogen cyanide (444) + TX, iodomethane (lUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (lUPAC name) (640) + TX, methyl bromide (537) + TX, norbormide (1318) + TX, phosacetim (1336) + TX, phosphine (lUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone (1341 ) + TX, potassium arsenite [CCN] + TX, pyrinuron (1371 ) + TX, scilliroside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851 ) and zinc phosphide (640) + TX,
a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)- ethyl piperonylate (lUPAC name) (934) + TX, 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2- enone (lUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB- 599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX, an animal repellent selected from the group of substances consisting of
anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171 ) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, methiocarb (530) + TX, pyridine- amine (lUPAC name) (23) + TX, thiram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX,
a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN] + TX,
a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX, and biologically active compounds selected from the group consisting of azaconazole (60207-31 -0] + TX, bitertanol [70585-36-3] + TX, bromuconazole [1 16255-48-2] + TX, cyproconazole [94361 -06-5] + TX, difenoconazole [1 19446-68-3] + TX, diniconazole [83657- 24-3] + TX, epoxiconazole [106325-08-0] + TX, fenbuconazole [1 14369-43-6] + TX, fluquinconazole [136426-54-5] + TX, flusilazole [85509-19-9] + TX, flutriafol [76674-21 -0] + TX, hexaconazole [79983-71 -4] + TX, imazalil [35554-44-0] + TX, imibenconazole [86598- 92-7] + TX, ipconazole [125225-28-7] + TX, metconazole [1251 16-23-6] + TX, myclobutanil [88671 -89-0] + TX, pefurazoate [101903-30-4] + TX, penconazole [66246-88-6] + TX, prothioconazole [178928-70-6] + TX, pyrifenox [88283-41 -4] + TX, prochloraz [67747-09-5] + TX, propiconazole [60207-90-1 ] + TX, simeconazole [149508-90-7] + TX, tebuconazole
[107534-96-3] + TX, tetraconazole [1 12281 -77-3] + TX, triadimefon [43121 -43-3] + TX, triadimenol [55219-65-3] + TX, triflumizole [99387-89-0] + TX, triticonazole [131983-72-7] + TX, ancymidol [12771 -68-5] + TX, fenarimol [60168-88-9] + TX, nuarimol [63284-71 -9] + TX, bupirimate [41483-43-6] + TX, dimethirimol [5221 -53-4] + TX, ethirimol [23947-60-6] + TX, dodemorph [1593-77-7] + TX, fenpropidine [67306-00-7] + TX, fenpropimorph [67564-91 -4] + TX, spiroxamine [1 18134-30-8] + TX, tridemorph [81412-43-3] + TX, cyprodinil [121552-61 -2] + TX, mepanipyrim [1 10235-47-7] + TX, pyrimethanil [531 12-28-0] + TX, fenpiclonil [74738- 17-3] + TX, fludioxonil [131341 -86-1] + TX, benalaxyl [71626-1 1 -4] + TX, furalaxyl [57646-30- 7] + TX, metalaxyl [57837-19-1 ] + TX, R-metalaxyl [70630-17-0] + TX, ofurace [58810-48-3] + TX, oxadixyl [77732-09-3] + TX, benomyl [17804-35-2] + TX, carbendazim [10605-21 -7] + TX, debacarb [62732-91 -6] + TX, fuberidazole [3878-19-1] + TX, thiabendazole [148-79-8] + TX, chlozolinate [84332-86-5] + TX, dichlozoline [24201 -58-9] + TX, iprodione [36734-19-7] + TX, myclozoline [54864-61 -8] + TX, procymidone [32809-16-8] + TX, vinclozoline [50471 -44- 8] + TX, boscalid [188425-85-6] + TX, carboxin [5234-68-4] + TX, fenfuram [24691 -80-3] + TX, flutolanil [66332-96-5] + TX, mepronil [55814-41 -0] + TX, oxycarboxin [5259-88-1 ] + TX, penthiopyrad [183675-82-3] + TX, thifluzamide [130000-40-7] + TX, guazatine [108173-90-6] + TX, dodine [2439-10-3] [1 12-65-2] (free base) + TX, iminoctadine [13516-27-3] + TX, azoxystrobin [131860-33-8] + TX, dimoxystrobin [149961 -52-4] + TX, enestroburin {Proc. BCPC, Int. Congr., Glasgow, 2003, 1 , 93} + TX, fluoxastrobin [361377-29-9] + TX, kresoxim- methyl [143390-89-0] + TX, metominostrobin [133408-50-1 ] + TX, trifloxystrobin [141517-21 - 7] + TX, orysastrobin [248593-16-0] + TX, picoxystrobin [1 17428-22-5] + TX, pyraclostrobin [175013-18-0] + TX, ferbam [14484-64-1 ] + TX, mancozeb [8018-01 -7] + TX, maneb [12427- 38-2] + TX, metiram [9006-42-2] + TX, propineb [12071 -83-9] + TX, thiram [137-26-8] + TX, zineb [12122-67-7] + TX, ziram [137-30-4] + TX, captafol [2425-06-1] + TX, captan [133-06- 2] + TX, dichlofluanid [1085-98-9] + TX, fluoroimide [41205-21 -4] + TX, folpet [133-07-3 ] + TX, tolylfluanid [731 -27-1] + TX, bordeaux mixture [801 1 -63-0] + TX, copperhydroxid [20427- 59-2] + TX, copperoxychlorid [1332-40-7] + TX, coppersulfat [7758-98-7] + TX, copperoxid [1317-39-1] + TX, mancopper [53988-93-5] + TX, oxine-copper [10380-28-6] + TX, dinocap [131 -72-6] + TX, nitrothal-isopropyl [10552-74-6] + TX, edifenphos [17109-49-8] + TX, iprobenphos [26087-47-8] + TX, isoprothiolane [50512-35-1 ] + TX, phosdiphen [36519-00-3] + TX, pyrazophos [13457-18-6] + TX, tolclofos-methyl [57018-04-9] + TX, acibenzolar-S- 5 methyl [135158-54-2] + TX, anilazine [101 -05-3] + TX, benthiavalicarb [413615-35-7] + TX, blasticidin-S [2079-00-7] + TX, chinomethionat [2439-01 -2] + TX, chloroneb [2675-77-6] + TX, chlorothalonil [1897-45-6] + TX, cyflufenamid [180409-60-3] + TX, cymoxanil [57966-95- 7] + TX, dichlone [117-80-6] + TX, diclocymet [139920-32-4] + TX, diclomezine [62865-36-5] + TX, dicloran [99-30-9] + TX, diethofencarb [87130-20-9] + TX, dimethomorph [110488-70-
10 5] + TX, SYP-LI90 (Flumorph) [211867-47-9] + TX, dithianon [3347-22-6] + TX, ethaboxam
[162650-77-3] + TX, etridiazole [2593-15-9] + TX, famoxadone [131807-57-3] + TX, fenamidone [161326-34-7] + TX, fenoxanil [115852-48-7] + TX, fentin [668-34-8] + TX, ferimzone [89269-64-7] + TX, fluazinam [79622-59-6] + TX, fluopicolide [2391 10-15-7] + TX, flusulfamide [106917-52-6] + TX, fenhexamid [126833-17-8] + TX, fosetyl-aluminium [39148-
15 24-8] + TX, hymexazol [10004-44-1 ] + TX, iprovalicarb [140923-17-7] + TX, IKF-916
(Cyazofamid) [120116-88-3] + TX, kasugamycin [6980-18-3] + TX, methasulfocarb [66952- 49-6] + TX, metrafenone [220899-03-6] + TX, pencycuron [66063-05-6] + TX, phthalide
[27355-22-2] + TX, polyoxins [1 1 1 13-80-7] + TX, probenazole [27605-76-1 ] + TX, propamocarb [25606-41 -1] + TX, proquinazid [189278-12-4] + TX, pyroquilon [57369-32-1 ] +
20 TX, quinoxyfen [124495-18-7] + TX, quintozene [82-68-8] + TX, sulfur [7704-34-9] + TX, tiadinil [223580-51 -6] + TX, triazoxide [72459-58-6] + TX, tricyclazole [41814-78-2] + TX, triforine [26644-46-2] + TX, validamycin [37248-47-8] + TX, zoxamide (RH7281 ) [156052-68- 5] + TX, mandipropamid [374726-62-2] + TX, isopyrazam [881685-58-1] + TX, sedaxane [874967-67-6] + TX, 3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxylic acid (9-
25 dichloromethylene-1 ,2,3,4-tetrahydro-1 ,4-methano-naphthalen-5-yl)-amide (dislosed in WO 2007/048556) + TX, 3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxylic acid (3',4',5'- trifluoro-biphenyl-2-yl)-amide (disclosed in WO 2006/087343) + TX,
[(3S,4R,4aR,6S,6aS, 12R, 12aS, 12bS)-3-[(cyclopropylcarbonyl)oxy]- 1 ,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-1 1 -oxo-9-(3-
30 pyridinyl)-2/-/,1 1 /-/naphtho[2,1 -b]pyrano[3,4-e]pyran-4-yl]methyl-cyclopropanecarboxylate
[915972-17-7] + TX and 1 ,3,5-trimethyl-N-(2-methyl-1 -oxopropyl)-N-[3-(2-methylpropyl)-4- [2,2,2-trifluoro-1 -methoxy-1 -(trifluoromethyl)ethyl]phenyl]-1 H-pyrazole-4-carboxamide
[926914-55-8] + TX,
or a biologically active compound selected from the group consisting of N-[(5-chloro- 35 2-isopropyl-phenyl)methyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1 -methyl-pyrazole-4- carboxamide + TX, 2,6-Dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)- tetrone + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol- 3-amine + TX, 3-(difluoromethyl)-N-(7-fluoro-1 ,1 ,3-trimethyl-indan-4-yl)-1 -methyl-pyrazole-4- carboxamide + TX, CAS 850881 -30-0 + TX, 3-(3,4-dichloro-1 ,2-thiazol-5-ylmethoxy)-1 ,2- benzothiazole 1 ,1 -dioxide + TX, 2-[2-[(2,5-dimethylphenoxy)methyl]phenyl]-2-methoxy-N- methyl-acetamide + TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1 -yl)quinolone + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol + TX, Oxathiapiprolin + TX, tert-butyl N-[6-[[[(1 -methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2- pyridyl]carbamate + TX, N-[2-(3,4-difluorophenyl)phenyl]-3-(trifluoromethyl)pyrazine-2- carboxamide + TX, 3-(difluoromethyl)-1 -methyl-N-[(3R)-1 ,1 ,3-trimethylindan-4-yl]pyrazole-4- carboxamide + TX, 2,2,2-trifluoroethyl N-[2-methyl-1 -[[(4- methylbenzoyl)amino]methyl]propyl]carbamate + TX, (2RS)-2-[4-(4-chlorophenoxy)-a,a,o trifluoro-o-tolyl]-1 -(1 H-1 ,2,4-triazol-1 -yl)propan-2-ol + TX, (2RS)-2-[4-(4-chlorophenoxy)- a,a,a-trifluoro-o-tolyl]-3-methyl-1 -(1 H-1 ,2,4-triazol-1 -yl)butan-2-ol + TX, 2-(difluoromethyl)-N- [(3R)-3-ethyl-1 ,1 -dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, N'-(2,5-dimethyl-4- phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5- dimethyl-phenyl]-N-ethyl-N-methyl-formamidine + TX, [2-[3-[2-[1 -[2-[3,5- bis(difluoromethyl)pyrazol-1 -yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3- chloro-phenyl] methanesulfonate + TX, but-3-ynyl N-[6-[[(Z)-[(1 -methyltetrazol-5-yl)-phenyl- methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, methyl N-[[5-[4-(2,4- dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate + TX, 3-chloro-6-methyl-5- phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5- phenyl-pyridazine + TX, 3-(difluoromethyl)-1 -methyl-N-[1 ,1 ,3-trimethylindan-4-yl]pyrazole-4- carboxamide + TX, 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4- methyl-tetrazol-5-one + TX, 1 -methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1 - l)phenoxy]methyl]phenyl]tetrazol-5-one + TX, and
Figure imgf000066_0001
The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number. The above described mixing partners are known. Where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop
Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound "abamectin" is described under entry number (1 ). Where "[CCN]" is added hereinabove to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995-2004]; for example, the compound "acetoprole" is described under the internet address http://www.alanwood.net pesticides/acetoprole.html.
Most of the active ingredients described above are referred to hereinabove by a so- called "common name", the relevant "ISO common name" or another "common name" being used in individual cases. If the designation is not a "common name", the nature of the designation used instead is given in round brackets for the particular compound; in that case, the lUPAC name, the lUPAC/Chemical Abstracts name, a "chemical name", a "traditional name", a "compound name" or a "develoment code" is used or, if neither one of those designations nor a "common name" is used, an "alternative name" is employed. "CAS Reg. No" means the Chemical Abstracts Registry Number.
The active ingredient mixture of the compounds of formula I selected from A1 to A18 (above) with active ingredients described above comprises a compound selected from A1 to A18 (above) and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1 :6000, especially from 50:1 to 1 :50, more especially in a ratio of from 20:1 to 1 :20, even more especially from 10:1 to 1 :10, very especially from 5:1 and 1 :5, special preference being given to a ratio of from 2:1 to 1 :2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1 :1 , or 5:1 , or 5:2, or 5:3, or 5:4, or 4:1 , or 4:2, or 4:3, or 3:1 , or 3:2, or 2:1 , or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1 :150, or 1 :35, or 2:35, or 4:35, or 1 :75, or 2:75, or 4:75, or 1 :6000, or 1 :3000, or 1 :1500, or 1 :350, or 2:350, or 4:350, or 1 :750, or 2:750, or 4:750. Those mixing ratios are by weight.
The mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.
The mixtures comprising a compound of formula I selected from A1 to A18 (above) and one or more active ingredients as described above can be applied, for example, in a single "ready-mix" form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula I selected from A1 to A18 (above) and the active ingredients as described above is not essential for working the present invention. The compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of the compounds I for the preparation of these compositions are also a subject of the invention.
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. 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 application methods for the compositions, that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention. Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The rate of application per hectare is preferably 1 g to 2000 g of active ingredient per hectare, more preferably 10 to 1000 g/ha, most preferably 10 to 600 g/ha. When used as seed drenching agent, convenient dosages are from 10mg to 1 g of active substance per kg of seeds.
When the combinations of the present invention are used for treating seed, 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.
Suitably, a composition comprising a compound of formula (I) according to the present invention is applied either preventative, meaning prior to disease development or curative, meaning after disease development.
The 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), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
Such 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). Also 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. the ondensation product of formaldehyde with naphthalene sulphonate, an alkylarylsulphonate, a lignin sulphonate, a fatty alkyl sulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol.
A seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds. Such seed dressing formulations are known in the art. Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g. as slow release capsules or microcapsules.
In general, 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.
Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.
EXAMPLES
The Examples which follow serve to illustrate the invention. Certain compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1 .5 ppm, 0.8 ppm or 0.2 ppm.
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 methods are:
Method G:
Spectra were recorded on a Mass Spectrometer (ACQUITY UPLC) from Waters (SQD, SQDII 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 μπι, 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: 10-100% B in 1 .2 min; Flow (ml/min) 0.85
Method H:
Spectra were recorded on a Mass Spectrometer (ACQUITY UPLC) from Waters
(SQD, SQDII 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 μπι, 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: 10-100% B in 2.7 min; Flow (ml/min) 0.85
Formulation Examples
Wettable powders a) b) c) active ingredient [compound of formula (I)] 25 % 50 % 75 %
sodium lignosulfonate 5 % 5 %
sodium lauryl sulfate 3 % - 5 %
sodium diisobutylnaphthalenesulfonate 6 % 10 % phenol polyethylene glycol ether - 2 %
(7-8 mol of ethylene oxide)
highly dispersed silicic acid 5 % 10 % 10 %
Kaolin 62 % 27 %
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 % 75 %
light mineral oil 5 % 5 % 5 %
highly dispersed silicic acid 5 % 5 % -
Kaolin 65 % 40 % -
Talcum - 20
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.
Emulsifiable concentrate
active ingredient [compound of formula (I)] 10 %
octylphenol polyethylene glycol ether 3 %
(4-5 mol of ethylene oxide)
calcium dodecylbenzenesulfonate 3 %
castor oil polyglycol ether (35 mol of ethylene oxide) 4 %
Cyclohexanone 30 %
xylene mixture 50 %
Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.
Dusts a) b) c)
Active ingredient [compound of formula (I)] 5 % 6 % 4 % talcum 95 %
Kaolin 94 %
mineral filler 96 %
Ready-for-use dusts are obtained by mixing active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders also be used for dry dressings for seed.
Extruder granules Active ingredient [compound of formula (I)] 15 %
sodium lignosulfonate 2 %
carboxymethylcellulose 1 %
Kaolin 82 %
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.
Coated granules
Active ingredient [compound of formula (I)] 8 %
polyethylene glycol (mol. wt. 200) 3 %
Kaolin 89 %
The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
Suspension concentrate
active ingredient [compound of formula (I)] 40 %
propylene glycol 10 %
nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
Sodium lignosulfonate 10 %
carboxymethylcellulose 1 %
silicone oil (in the form of a 75 % emulsion in water) 1 %
Water 32 %
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. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
Flowable concentrate for seed treatment
active ingredient [compound of formula (I)] 40 %
propylene glycol 5 %
copolymer butanol PO/EO 2 %
tristyrenephenole with 10-20 moles EO 2 %
1 ,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 % monoazo-pigment calcium salt 5 %
Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
Water 45.3 %
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. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
Slow Release Capsule Suspension
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.
Preparation examples
Example 1 : This example illustrates the preparation of 5-fluoro-3,3,4,4-tetramethyl-1 -(4- methylbenzimidazol-1 -yl)isoquinoline. Step 1 : Preparation of ethyl-2-(2-fluorophenyl)-2-methyl-propanoate
To a suspension of sodium hydride (0.69 mol, 27.4 g) in tetrahydrofuran (220 mL) at room temperature was added dropwise a solution of ethyl-2-(2-fluorophenyl)acetate (0.27 mol, 50.0 g) and iodomethane (0.82 mmol, 1 17.9 g) in tetrahydrofuran (60 mL, cone. Total 1 M) and the mixture was stirred at room temperature overnight. The reaction was quenched by the slow addition of a saturated aqueous solution ammonium chloride and then poured into 300 mL of ice-water mixture. The aqueous phase was extracted with ethyl acetate, and the combined organic extracts were dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography (heptane/ethyl acetate = 19:1 ) to give ethyl-2-(2-fluorophenyl)-2-methyl-propanoate as a pale yellow oil: LC-MS (Method H) UV Detection: 220 nm, Rt = 1 .60; MS: (M+1 ) = 21 1.2; 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1 .16 - 1 .23 (m, 3 H) 1 .57 (s, 6 H) 4.17 (d, J=6.97 Hz, 2 H) 6.99 - 7.05 (m, 1 H) 7.1 1 - 7.17 (m, 1 H) 7.22 - 7.28 (m, 1 H) 7.33 (td, J=7.89, 1 .83 Hz, 1 H); 19F NMR (377 MHz, CHLOROFORM-d) δ ppm -1 13.26 (s, 1 F).
Step 2: Preparation of 3-(2-fluorophenyl)-2,3-dimethyl-butan-2-ol
A solution of ethyl-2-(2-fluorophenyl)-2-methyl-propanoate (0.25 mol, 52.1 g) and
lanthanum(lll) chloride bis(lithium chloride) complex (0.6 M in THF, 0.50 equiv., 0.12 mol, 207 mL) in tetrahydrofuran (1 .2 M) was stirred at room temperature for 1.5 h. The reaction was then cooled to 0 °C and a solution of methyl magnesium bromide (3.0 M in diethyl ether, 3.0 equiv, 0.74 mol, 248 mL) was subsequently added dropwise. The reaction mixture was stirred at room temperature overnight, cooled to 0 °C and then quenched by the dropwise addition of a saturated aqueous solution of ammonium chloride solution. Water was added and the reaction mixture was stirred for an additional 30 min. The reaction mixture was filtered over Celite and the two phases were separated. The aqueous phase was extracted with ie f-butyl methyl ether, and the combined organic phases were washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure to give 3-(2- fluorophenyl)^, 3-dimethyl-butan-2-ol as a yellowish solid: LC-MS (Method H) UV Detection: 220 nm, Rt = 1.46; MS: (M-OH) = 179.3; m.p. 42-43 °C; 1H NMR (400 MHz, CHLOROFORM- d) δ ppm 1 .19 (d, J=1.10 Hz, 6 H) 1.50 (d, J=2.93 Hz, 6 H) 6.97 - 7.04 (m, 1 H) 7.07 - 7.12 (m, 1 H) 7.18 - 7.24 (m, 1 H) 7.40 (td, J=8.25, 1 .83 Hz, 1 H); 19F NMR (377 MHz,
CHLOROFORM-d) δ ppm -104.04 (s, 1 F).
Step 3: Preparation of 5-fluoro-3,3,4,4-tetramethyl-1 -methylsulfanyl-isoquinoline.
To cooled (0 °C) sulfuric acid (98% w/w, 133 mL, 1 M) was added a mixture of methyl thiocyanate (133 mmol, 9.73 g) and 3-(2-fluorophenyl)-2,3-dimethyl-butan-2-ol (1.00 equiv., 133 mmol, 26.1 g) portion-wise over 15 min, and the mixture was stirred at room temperature for additional 20 min. The reaction mixture was carefully poured into 600ml ice water and the pH of the water layer was adjusted to ~8 using an aqueous solution of NaOH (30% w/w). The aqueous phase was extracted with ethyl acetate and the combined organic phases were dried with Na2S04, filtered and concentrated in vacuo to afford (25.1 g, 75 %) of 5-fluoro- 3,3,4,4-tetramethyl-1 -methylsulfanyl-isoquinoline as a pale yellow oil: LC-MS (Method G) UV Detection: 220 nm, Rt=; MS: (M+1 ) =; 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1 .10 (s, 6 H) 1 .24 (d, J=2.93 Hz, 6 H) 2.34 (s, 3 H) 7.00 (ddd, J=12.20, 8.34, 1.10 Hz, 1 H) 7.07 - 7.21 (m, 1 H) 7.32 - 7.42 (m, 1 H); 19F NMR (377 MHz, CHLOROFORM-d) δ ppm -1 1 1 .06 (s, 1 F).
Step 4: Preparation of 5-fluoro-3,3,4,4-tetramethyl-2H-isoquinolin-1 -one.
To a solution of 5-fluoro-3,3,4,4-tetramethyl-1 -methylsulfanyl-isoquinoline (99.8 mmol, 25.1 g) in a mixture of acetic acid (160 mL, 0.25 M) and water (40 mL) was added sodium acetate (0.10 equiv., 9.98 mmol, 0.818 g) and the mixture was heated at reflux for 2 h. The reaction mixture was then cooled down to room temperature and most of the acetic acid solution was removed under vacuo. The residue was then carefully added to a mixture of saturated aqueous NaHC03 and ethyl acetate. The two layers were separated and the aqueous layer was extracted with ethyl acetate. The combined organic phases were washed with saturated aqueous NaHC03, water and brine, dried with Na2S04, filtered and concentrated in vacuo to afford 5-fluoro-3,3,4,4-tetramethyl-2H-isoquinolin-1 -one (21 .4 g, 97%) as a pale yellow oil: LC-MS (Method G) UV Detection: 220 nm, Rt = 1.28; MS: (M+1 ) = 222.2; 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1 .21 (s, 6 H) 1 .36 (d, J=1.00 Hz, 6 H) 6.19 (br. s, 1 H) 7.12 (ddd, J=12.38, 8.34, 1 .28 Hz, 1 H) 7.20 - 7.26 (m, 1 H) 7.85 (dd, J=7.52, 1 .28 Hz, 1 H); 19F NMR (377 MHz, CHLOROFORM-d) δ ppm -1 1 1.05 (s, 1 F). Step 5: Preparation of 1 -chloro-5-fluoro-3,3,4,4-tetramethyl-isoquinoline.
To a solution of /V,/V-dimethylformamide (6.3 mmol, 0.49 mL) in dichloromethane (8 mL, 0.8 M) at room temperature was added oxalyl chloride (1 .3 equiv., 6.01 mmol, 0.53 mL) dropwise and the white suspension was vigorously stirred for 30 min. A solution of 5-fluoro-3, 3,4,4- tetramethyl-2H-isoquinolin-1 -one (4.52 mmol, 1.00 g) in dichloromethane (9 mL, 0.5 M) was then added dropwise and the mixture was stirred at room temperature for 2h. The reaction mixture was poured into an ice-cooled mixture of saturated aqueous NaHC03 solution and pentane, and the organic phase was separated. The aqueous phase was then extracted with pentane, and the combined organic phases were washed with brine, dried over Na2S04, filtered and concentrated to give 1 -chloro-5-fluoro-3,3,4,4-tetramethyl-isoquinoline (1 .02 g, 94 % yield) as a colourless oil: LC-MS (Method G) UV Detection: 220 nm, Rt= 1.16; MS: (M+1 ) = 240-242; 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1 .27 (s, 6 H) 1 .38 (s, 6 H) 7.15- 7.20 (m, 1 H) 7.26 - 7.36 (m, 1 H) 7.62 (d, 1 H). Step 6: Preparation of 5-fluoro-3,3,4,4-tetramethyl-1 -(4-methylbenzimidazol-1 -yl)isoquinoline. To a solution of 1 -chloro-5-fluoro-3,3,4,4-tetramethyl-isoquinoline (1 .67 mmol, 0.430 g) in pyridine (0.20 M, 9.0 mL) at room temperature was added 4-methyl-1 H-benzimidazole (1 .5 equiv., 2.69 mmol, 0.356 g) and the mixture was stirred at 90 °C for 15 hours. The reaction mixture was allowed to cool down to room temperature and then concentrated under vacuo. The residue obtained was purified by flash chromatography to give 5-fluoro-3,3,4,4- tetramethyl-1 -(4-methylbenzimidazol-1 -yl)isoquinoline (0.525 g, 87% yield) as a beige solid : mp= 1 18-120°C, LC-MS (Method G) UV Detection: 220 nm, Rt = 1 .19, MS: (M+1 ) = 336; 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1 .32 (s, 6 H) 1 .47 (s, 6 H) 2.71 (s, 3H) 6.91 -6.95 (m, 1 H) 7.10 - 7.25 (m, 5 H) 8.18 (s, 1 H).
Example 2: This example illustrates the preparation of 4,4-difluoro-3,3-dimethyl-1 -(4- methylbenzimidazol-1 -yl)isoquinoline
Step 1 : Preparation of 3,3-dimethyl-2H-isoquinoline-1 ,4-dione.
To a solution of 3,3-dimethyl-2,4-dihydroisoquinolin-1 -one (57.1 mmol, 10.0 g) in CCI4 (0.20 M, 285 mL) at room temperature was added N-bromosuccinimide (3.0 equiv., 171 mmol, 30.5 g) and AIBN (0.15 equiv., 8.5 mmol, 1 .43 g) and the reaction mixture was stirred at 70 °C for 3 hours. The reaction mixture was allowed to cool down to room temperature, concentrated under vacuo and diluted with EtOAc, washed with water and brine, dried over Na2S04, filtered and concentrated to give 4,4-dibromo-3,3-dimethyl-2H-isoquinolin-1 -one (25.2 g) as a light yellow solid which was used directly in the next step without further purification: LC-MS (Method H) UV Detection: 220 nm, Rt = 1.34; MS: (M+1 ) = 332-334-336; 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.57 (s, 6 H) 7.21 (br. s, 1 H) 7.70 - 7.77 (m, 1 H) 7.78 - 7.85 (m, 1 H) 8.06 - 8.14 (m, 1 H) 8.23 - 8.30 (m, 1 H).
To a solution of 4,4-dibromo-3,3-dimethyl-2H-isoquinolin-1 -one (20.0 g) in a mixture of water (450 mL) and tetrahydrofuran (225 mL) was added sodium carbonate (3.0 equiv., 135 mmol, 14.3 g) and the mixture was stirred at room temperature for 12 h and at 70 °C for 4 h 30 min. The reaction mixture was allowed to cool down to room temperature, diluted with water, acidified to PH 3-4 with 90 mL of a 2 M solution of hydrochloric acid and extracted with dichloromethane. The combined organic extracts were dried over Na2S04, filtered and concentrated to give 3,3-dimethyl-2H-isoquinoline-1 ,4-dione (9.95 g) as a yellow solid: LC- MS (Method H) UV Detection: 220 nm, Rt = 0.81 ; MS: (M+1 ) = 190; 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.77 (s, 3 H) 1.97 (s, 3 H) 7.39 (s, 1 H) 7.46 - 7.58 (m, 1 H) 7.60 - 7.71 (m, 1 H) 7.98 - 8.22 (m, 2 H).
Step 2: Preparation of 1 -chloro-3,3-dimethyl-isoquinolin-4-one. To a solution of Λ/,/V-dimethylformamide (2.3 mL, 30 mmol) in dichloromethane (52 mL, 0.6 M) at room temperature was added oxalyl chloride (0.67 equiv., 20 mmol, 1 .8 mL) dropwise over a period of 35 min and the white suspension was vigorously stirred for 15 min until the gas evolution stopped. A solution of 3,3-dimethyl-2H-isoquinoline-1 ,4-dione (2.5 g, 13 mmol) in dichloromethane (25 mL) was then added dropwise and the mixture was stirred at room temperature for 1 h. The reaction mixture was poured into an ice-cooled mixture of saturated aqueous NaHC03 solution and pentane, and the organic phase was separated. The aqueous phase was then extracted with pentane, and the combined organic phases were washed with brine, dried over Na2S04, filtered and concentrated to give 1 -chloro-3,3-dimethyl-isoquinolin- 4-one (2.5 g, 91 % yield) as a yellow solid: LC-MS (Method H) UV Detection: 220 nm, Rt= 1.34; MS: (M+1 ) = 208-210; 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1 .47 (s, 6 H) 7.62 - 7.69 (m, 1 H) 7.73 - 7.81 (m, 1 H) 7.90 (dd, J=8.07, 0.73 Hz, 1 H) 8.04 (dd, J=7.50, 0.90 Hz, 1 H). Step 3: Preparation of 3,3-dimethyl-1 -(4-methylbenzimidazol-1 -yl)isoquinolin-4-one.
To a solution of 1 -chloro-3,3-dimethyl-isoquinolin-4-one (3.61 mmol, 0.750 g) in pyridine (0.07 M, 50 mL) at room temperature was added 4-methyl-1 H-benzimidazole (1 .5 equiv., 0.716 g, 5.42 mmol) and the mixture was stirred at 100 °C for 15 hours. The reaction mixture was allowed to cool down to room temperature and then concentrated under vacuo. The residue obtained was purified by flash chromatography to give 3,3-dimethyl-1 -(4- methylbenzimidazol-1 -yl)isoquinolin-4-one (0.569 g, 52% yield) as a brown oil: LC-MS (Method G) UV Detection: 220 nm, Rt = 0.98, MS: (M+1 ) = 305; 1H NMR (400 MHz,
CHLOROFORM-d) δ ppm 1.63 (s, 6 H) 2.75 (s, 3 H) 7.15 - 7.27 (m, 3 H) 7.36 - 7.42 (m, 1 H) 7.70 - 7.82 (m, 2 H) 8.18 - 8.25 (m, 1 H) 8.28 (s, 1 H).
Step 4: Preparation of 4,4-difluoro-3,3-dimethyl-1 -(4-methylbenzimidazol-1 -yl)isoquinoline.
A solution of 3,3-dimethyl-1 -(4-methylbenzimidazol-1 -yl)isoquinolin-4-one (1 .85 mmol, 560 mg) in 2,2-difluoro-1 ,3-dimethyl-imidazolidine (10.0 equiv., 18.5 mmol, 2.4 mL) was stirred at 105 °C overnight. The reaction mixture was allowed to cool down to room temperature, diluted with DCM then quenched by slow addition to a saturated aqueous NaHC03 solution. The 2 phases were separated, and the aqueous phase was extracted with DCM. The combined organic phases were washed with brine, dried over Na2S04, filtered and concentrated. The residue was purified by flash chromatography to give 4,4-difluoro-3,3- dimethyl-1 -(4-methylbenzimidazol-1 -yl)isoquinoline (36 mg, 60% yield) as a white solid: LC- MS (Method G) UV Detection: 220 nm, Rt = 1 .12; MS: (M+1 ) = 326; mp 142 - 149 °C; 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.49 (s, 6 H) 2.76 (s, 3 H) 7.15 - 7.27 (m, 2 H) 7.34 - 7.42 (m, 2 H) 7.57 - 7.64 (m, 1 H) 7.71 - 7.79 (m, 1 H) 7.90 - 7.97 (m, 1 H) 8.31 (s, 1 H); 19F NMR (377 MHz, CHLOROFORM-d) δ ppm-1 12.38 (br. s., 1 F).
Example 3: This example illustrates the preparation of 1 '-(benzimidazol-1 -yl)-3',3'-dimethyl- spiro(cyclopropane-1 ,4'-isoquinoline)
Step 1 : Preparation of 3,3-dimethylspiro(2H-isoquinoline-4,1 '-cyclopropane)-1 -one.
In an autoclave was added a solution of 2-(1 -phenylcyclopropyl)propan-2-amine (120mg, 0.685 mmol), benzoquinone (2.0 equiv., 1.37 mmol, 153 mg) and palladium (II) acetate (0.05 equiv., 0.034 mmol, 7.6 mg) in acetic acid (4.6 mL, 0.15 M) and the high pressure reactor was pressurized with carbon monoxide (3 bars) and heated at 1 10°C overnight. The reaction vessel was allowed to cool down to room temperature, depressurized and the reaction mixture was diluted with dichloromethane and quenched by the addition of an aqueous NaOH solution (2.0 M) to reach pH>9. The two phases were separated and the aqueous phase was extracted with dichloromethane twice. The combined organic phases were washed with brine, dried over Na2S04, filtered, concentrated and purified by flash chromatography to give 3,3-dimethylspiro(2H-isoquinoline-4,1 '-cyclopropane)-1 -one (27 mg, 20 % yield) as a yellowish gum: LC-MS (Method G), Rt= 0.80; MS: (M+1 ) = 202; 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.96 (t, 2 H) 1 .10 (t, 2H) 1 .18 (s, 6 H) 6.21 (NH, 1 H) 6.91 (d, 1 H) 7.20 (t, 1 H) 7.45 (t, 1 H) 8.09 (d, 1 H).
Step 2: Preparation of 1 '-chloro-3',3'-dimethyl-spiro(cyclopropane-1 ,4'-isoquinoline). To a solution of /V,/V-dimethylformamide (0.63 mmol, 0.049 mL) in dichloromethane (1 mL, 0.5 M) at room temperature was added oxalyl chloride (1.3 equiv., 0.63 mmol, 0.056 mL) dropwise and the white suspension was vigorously stirred for 30 min. A solution of 3,3- dimethylspiro(2H-isoquinoline-4,1 '-cyclopropane)-1 -one (0.423 mmol, 85 mg) in
dichloromethane (0.8 mL, cone, total 0.25 M) was then added dropwise and the mixture was stirred at room temperature for 1 h. The reaction mixture was poured into an ice-cooled mixture of saturated aqueous NaHC03 solution and pentane, and the organic phase was separated. The aqueous phase was then extracted with pentane, and the combined organic phases were washed with brine, dried over Na2S04, filtered and concentrated to give 1 '- chloro-3',3'-dimethyl-spiro(cyclopropane-1 ,4'-isoquinoline) (101 mg, 98 % yield) as a beige liquid : LC-MS (Method G), Rt= 1.06; MS: (M+1 ) = 220-222.
Step 3: Preparation of 1 '-(benzimidazol-1 -yl)-3',3'-dimethyl-spiro(cyclopropane-1 ,4'- isoquinoline). To a solution of 1 '-chloro-3',3'-dimethyl-spiro(cyclopropane-1 ,4'-isoquinoline) (0.064 mmol, 14 mg) in pyridine (1.3 mL, 0.05M) was added benzimidazole (5 equiv., 0.32 mmol, 38 mg) and the mixture was stirred at 90 °C for 1 h. The reaction mixture was allowed to cool down to room temperature and then concentrated under vacuo. The residue obtained was purified by flash chromatography to give 1 '-(benzimidazol-1 -yl)-3',3'-dimethyl-spiro(cyclopropane- 1 ,4'-isoquinoline) (9 mg, 50 % yield) as a yellow gum : LC-MS (Method G), t= 1 .04; MS: (M+1 ) = 302; 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1 .01 (t, 2 H) 1 .17 (t, 2H) 1 .23 (s, 6 H) 7.08 (d, 1 H) 7.15-7.24 (m, 2H) 7.27-7.35 (m, 2 H) 7.48 (t, 1 H) 7.52 (d, 1 H) 7.84 (d, 1 H) 8.30 (s, 1 H).
Table E: Physical data of compounds of formula I
Entry STRUCTURE RT (min) [M+H] Method MP °C
(measured)
E-1 1 .15 336.4 G 45 - 46
E-2 1 .13 322.5 G
E-3 1 .04 302 G
E-4 1 .22 401.3 G 48 - 49
E-5 1 .25 390.5 G
F f
Figure imgf000081_0001
E-14 1.25 350.5 G 87-88
E-15 1.10 326 G
E-16 1.14 318 G
E-17 1.21 356.4 G 50-51
E-18 1.19 350.6 G
E-19 1.13 358 G 157-159
E-20 1.08 344 G
E-21 1.14 340.5 G
E-22 1.18 354.5 G E-23 1.13 340.5 G 132-133
E-24 1.10 380.4 G 178-179
Figure imgf000083_0001
E-25 0.99 318.4 G 159-161
E-26 1.03 318.5 G 96-101
E-27 1.07 332.5 G 145-149
E-28 1.81 347 H 199-202
E-29 1.51 325 H
CI
Figure imgf000084_0001
Figure imgf000085_0001
E-43 1.12 302 G 132-133
E-44 1.07 290 G
E-45 1.27 370 G 147-151
E-46 1.21 354 G 122-125
E-47 1.99 361 H
E-48 2.06 379 H
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Biological examples
Botryotinia fuckeliana (Botrytis cinerea) I liquid culture (Gray mould)
Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth
(Vogels 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 3-4 days after application.
The following compounds of Table E gave at least 80% disease control at 200 ppm when compared to untreated control leaf disks under the same conditions, which show extensive disease development: E-1 , E-2, E-3, E-4, E-5, E-6, E-7, E-8, E-9, E-10, E-1 1 , E- 12, E-13, E-14, E-15, E-16, E-17, E-18, E-19, E-20, E-21 , E-22, E-23, E-25, E-26, E-27, E- 29, E-30, E-31 , E-32, E-33, E-34, E-35, E-36, E-37, E-38, E-39, E-40, E-41 , E-42, E-43, E- 44, E-45, E-46, E-47, E-48, E-49, E-50, E-51 , E-52, E-53, E-54, E-55, E-56, E-57, E-58, E- 59, E-60, E-61
Fusarium culmorum I liquid culture (Head blight)
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 3-4 days after application.
The following compounds of Table E gave at least 80% disease control at 200 ppm when compared to untreated control leaf disks under the same conditions, which show extensive disease development: E-1 , E-2, E-4, E-7, E-9, E-14, E-15, E-16, E-17, E-18, E-19, E-20, E-21 , E-22, E-23, E-25, E-26, E-27, E-30, E-31 , E-32, E-33, E-34, E-35, E-36, E-41 , E- 42, E-45, E-46, E-47, E-48, E-49, E-50, E-51 , E-55, E-56, E-57, E-58, E-59, E-60, E-61 Gaeumannomyces praminis / liquid culture (Take-all of cereals)
Mycelial fragments of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores iss added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4-5 days after application.
The following compounds of Table E gave at least 80% disease control at 200 ppm when compared to untreated control leaf disks under the same conditions, which show extensive disease development: E-1 , E-3, E-4, E-7, E-8, E-9, E-14, E-15, E-16, E-17, E-18, E-19, E-21 , E-23, E-30, E-31 , E-32, E-33, E-37, E-41 , E-47, E-48, E-49, E-51 , E-58, E-59, E- 60, E-61 Glomerella lagenarium (Colletotrichum lagenarium) I liquid culture (Anthracnose)
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 measured photometrically 3-4 days after application.
The following compounds of Table E gave at least 80% disease control at 200 ppm when compared to untreated control leaf disks under the same conditions, which show extensive disease development: E-1 , E-2, E-3, E-4, E-5, E-6, E-7, E-8, E-9, E-10, E-1 1 , E-
12, E-13, E-14, E-15, E-16, E-17, E-18, E-19, E-20, E-21 , E-22, E-23, E-25, E-26, E-27, E- 30, E-31 , E-32, E-33, E-38, E-39, E-40, E-41 , E-42, E-43, E-44, E-45, E-46, E-49, E-50, E-
54, E-55, E-56, E-57, E-58, E-59, E-60, E-61
Monographella nivalis (Microdochium nivale) I liquid culture (foot rot cereals)
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.
The following compounds of Table E gave at least 80% disease control at 200 ppm when compared to untreated control leaf disks under the same conditions, which show extensive disease development: E-1 , E-2, E-4, E-5, E-6, E-7, E-8, E-9, E-10, E-1 1 , E-12, E-
13, E-14, E-15, E-16, E-17, E-18, E-19, E-20, E-21 , E-22, E-23, E-25, E-26, E-27, E-30, E- 31 , E-32, E-33, E-34, E-37, E-38, E-39, E-40, E-41 , E-42, E-43, E-44, E-45, E-46, E-47, E- 48, E-49, E-50, E-51 , E-53, E-54, E-55, E-56, E-57, E-58, E-59, E-60, E-61
Mvcosphaerella graminicola (Septoria tritici) I liquid culture (Septoria blotch) 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.
The following compounds of Table E gave at least 80% disease control at 200 ppm when compared to untreated control leaf disks under the same conditions, which show extensive disease development: E-1 , E-18, E-21 , E-22, E-30, E-32, E-33, E-34, E-35, E-36, E-50, E-53, E-54, E-55, E-56, E-57, E-60
Magnaporthe grisea (Pyricularia oryzae) I rice / leaf disc preventative (Rice Blast)
Rice leaf segments cv. Ballila are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf segments are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf segments are incubated at 22°C and 80% r.h. 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 segments (5 - 7 days after application).
The following compounds of Table E gave at least 80% disease control at 200 ppm when compared to untreated control leaf disks under the same conditions, which show extensive disease development: E-21 , E-42, E-49, E-50
Magnaporthe grisea (Pyricularia oryzae) I liquid culture (Rice Blast)
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 3-4 days after application.
The following compounds gave at least 80% control of Magnaporthe grisea at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development:: E-1 , E-4, E-5, E-6, E-7, E-8, E-9, E-10, E-1 1 , E-12, E-13, E-14, E-15, E-16, E-17, E-18, E-19, E-20, E-21 , E-22, E-23, E-24, E-25, E-26, E-27, E-30, E-31 , E-32, E- 33, E-34, E-35, E-36, E-37, E-38, E-39, E-40, E-41 , E-42, E-43, E-44, E-45, E-46, E-47, E- 48, E-49, E-50, E-51 , E-52, E-53, E-54, E-55, E-56, E-57, E-58, E-59, E-60, E-61
Fusarium culmorum I wheat / spikelet preventative (Head blight) Wheat spikelets cv. Monsun are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The spikelets are inoculated with a spore suspension of the fungus 1 day after application. The inoculated spikelets are incubated at 20 °C and 60% rh under a light regime of 72 h semi 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 spikelets (6 - 8 days after application).
The following compounds gave at least 80% control of Fusarium culmorum at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: E-20, E-46, E-49, E-56, E-58
Pyrenophora teres I barley / leaf disc preventative (Net blotch)
Barley leaf segments cv. Hasso are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf segmens are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf segments are incubated at 20 °C and 65% 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 disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 - 7 days after application).
The following compounds gave at least 80% control of Pyrenophora teres at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: E-16
Pyrenophora teres I liquid culture (Net blotch)
Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth
(Vogels 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 3-4 days after application.
The following compounds gave at least 80% control of Pyrenophora teres at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: E-1 , E-4, E-5, E-6, E-7, E-9, E-10, E-1 1 , E-12, E-13, E-14, E-15, E-16, E-17, E-18, E-19, E-20, E-21 , E-22, E-23, E-25, E-26, E-27
Sclerotinia sclerotiorum I liquid culture (cottony rot) Mycelia fragments of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (Vogels broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format) the nutrient broth containing the fungal material is added. The test plates are incubated at 24 °C and the inhibition of growth is determined
photometrically 3-4 days after application.
The following compounds gave at least 80% control of Sclerotinia sclerotiorum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: E-1 , E-15, E-16, E-17, E-18, E-19, E-20, E-21 , E-22, E-23, E-25, E-26, E-27, E-30, E-31 , E-32, E-33, E-37, E-38, E-39, E-40, E-41 , E-42, E-43, E-44, E- 45, E-46, E-55, E-56, E-57, E-58, E-61

Claims

A compound of formula I:
Figure imgf000094_0001
wherein
Ri and R2 are each independently selected from hydrogen, cyano, Ci-C6 alkyl, C3-C7 cycloalkyi, C2-C6 alkenyl and C2-C6 alkynyl, in which the alkyl, cycloalkyi, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C6 alkoxy and Ci-C6 alkylthio; or
Ri and R2 together with the carbon atom to which they are attached represent a C3- Cio cycloalkyi group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, Ci-C6 alkyl, Ci-C6 alkoxy and Ci-C6 alkylthio);
R3 and R4 are each independently selected from hydrogen, halogen, hydroxyl, Ci-C6 alkyl, CrC6 alkoxy, C3-C7 cycloalkyi, C2-C6 alkenyl and C2-C6 alkynyl, in which the alkyl, alkoxy, cycloalkyi, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C6 alkoxy and Ci-C6 alkylthio; or
R3 and R4 together with the carbon atom to which they are attached represent C=0, C=NORa, C=C(Rb)(Rc) or C3-Ci0 cycloalkyi (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of a halogen, d- C6 alkyl, CrC6 alkoxy and Ci-C6 alkylthio); or
R2 and R3 together with the carbon atoms to which they are attached represent a C5- Cio cycloalkyi (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, Ci-C6 alkyl, Ci-C6 alkoxy and Ci-C6 alkylthio, and, additionally, a ring carbon unit may be replaced by an oxygen or sulphur atom);
each R5 independently represents halogen, hydroxyl, mercapto, nitro, cyano, formyl, Ci-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyi, CrC6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C C6 alkylthio, -C(=NORa)CrC6alkyl, C C6
alkylcarbonyl, aryl, heteroraryl, aryloxy or heteroraryloxy, in which the alkyl, cycloalkyi, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, aryl and heteroaryl groups may be optionally substituted with 1 to 5 substituents independently selected from halogen, Ci-C6 alkyl, CrC6 alkoxy, cyano and Ci-C6 alkylthio; n is 0, 1 , 2, 3 or 4; R6 is hydrogen, halogen, CrC6 alkyl or CrC6 alkoxy;
each R7 independently represents hydroxyl, mercapto, cyano, halogen, Ci-C6 alkyl, Ci-C6 haloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 haloalkenyl, C3-C6 haloalkynyl, Ci-C6 alkylthio, CrC6 haloalkoxy, CrC6 haloalkylthio, CrC6 alkoxycarbonyl, CrC6 alkylcarbonyl, C3-C7 cycloalkyi, CrC6 alkoxy, C3-C6 alkenyloxy or C3-C6 alkynyloxy; m is 0, 1 , 2, 3 or 4; or
Two adjacent R7 subsitutents together with the carbon atoms to which they are attached represent a C5-C7 cycloalkyi (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, Ci-C6 alkyl, Ci-C6 alkoxy and Ci-C6 alkylthio, and, additionally, a ring carbon unit may be replaced by an oxygen or sulphur atom);
Ra is selected from hydrogen, Ci-C6 alkyl, C3-C7 cycloalkyi, C3-C6 alkenyl and C3-C6 alkynyl, in which the alkyl, cycloalkyi, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C6 alkoxy and Ci-C6 alkylthio;
Rb and Rc are each independently selected from hydrogen, halogen, cyano, Ci-C6 alkyl, C3-C7 cycloalkyi, C2-C6 alkenyl, C2-C6 alkynyl, CrC6 alkoxy and CrC6 alkylthio, in which the alkyl, cycloalkyi, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C6 alkoxy and Ci-C6 alkylthio; or a salt or N-oxide thereof.
A compound according to claim 1 wherein R-i and R2 are each independently selected from hydrogen, CrC6 alkyl and C3-C7 cycloalkyi, in which the alkyl and cycloalkyi groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, CrC6 alkoxy and Ci-C6 alkylthio; or
Ri and R2 together with the carbon atom to which they are attached represent a C3-C6 cycloalkyi group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, Ci-C6 alkyl, Ci-C6 alkoxy and Ci-C6 alkylthio); or
R2 and R3 together with the carbon atoms to which they are attached represent a C5- C7 cycloalkyi (which may be optionally substituted with 1 to 3 substituents
independently selected from the group consisting of halogen, Ci-C6 alkyl, Ci-C6 alkoxy and Ci-C6 alkylthio, and, additionally, a ring carbon unit may be replaced by an oxygen or sulphur atom).
A compound according to claim 1 or 2 wherein R3 and R4 are each independently selected from hydrogen, halogen, hydroxyl, Ci-C6 alkyl, CrC6 alkoxy and C3-C7 cycloalkyl, in which the alkyl, alkoxy and cycloalkyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C6 alkoxy and Ci-C6 alkylthio; or
R3 and R4 together with the carbon atom to which they are attached represent C=0, C=NORa, C=C(Rb)(Rc) or C3-C6 cycloalkyl (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of a halogen, d- C6 alkyl, CrC6 alkoxy and Ci-C6 alkylthio); or
R2 and R3 together with the carbon atoms to which they are attached represent a C5- Cj cycloalkyl (which may be optionally substituted with 1 to 3 substituents
independently selected from the group consisting of halogen, Ci-C6 alkyl, Ci-C6 alkoxy and Ci-C6 alkylthio, and, additionally, a ring carbon unit may be replaced by an oxygen or sulphur atom).
A compound according to any one of claims 1 , 2 or 3 wherein each R5 independently represents halogen, cyano, Ci-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, Ci-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, CrC6 alkylthio, -
Figure imgf000096_0001
phenyl, heteroraryl (wherein heteroaryl is pyridyl, thiophenyl, thiazolyl, imidazolyl or oxazolyl), phenoxy or heteroraryloxy (wherein heteroaryl is pyridyl, thiophenyl, thiazolyl, imidazolyl or oxazolyl), in which the alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, phenyl and heteroaryl groups may be optionally substituted with 1 to 5 substituents independently selected from halogen, Ci-C6 alkyl, CrC6 alkoxy, cyano and Ci-C6 alkylthio; n is 0, 1 , 2, 3 or 4.
A compound according to any one of claims 1 , 2, 3 or 4 wherein R6 is hydrogen, halogen or Ci-C6 alkyl.
A compound according to any one of claims 1 , 2, 3, 4, or 5 wherein each R7 independently represents cyano, halogen, Ci-C6 alkyl, Ci-C6 haloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 haloalkenyl, C3-C6 haloalkynyl, CrC6 alkylthio, CrC6 haloalkoxy, Ci-C6 haloalkylthio, C3-C7 cycloalkyl, CrC6 alkoxy, C3-C6 alkenyloxy or C3-C6 alkynyloxy; m is 0, 1 , 2, 3 or 4; or Two adjacent R7 substituents together with the carbon atoms to which they are attached represent a C5-C7 cycloalkyi group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, Ci- Ce alkyl, CrC6 alkoxy and Ci-C6 alkylthio, and, additionally, a ring carbon unit may be replaced by an oxygen or sulphur atom).
7. A compound according to any one of claims 1 , 2, 3, 4, 5, or 6 wherein R-i and R2 are each independently selected from hydrogen and Ci-C4 alkyl, in which the alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C3 alkoxy and C1-C3 alkylthio; or
Ri and R2 together with the carbon atom to which they are attached represent a C3-C6 cycloalkyi group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, C1-C3 alkyl, C C3 alkoxy and C C3 alkylthio).
8. A compound according to any one of claims 1 , 2, 3, 4, 5, 6, or 7 wherein R3 and R4 are each independently selected from hydrogen, halogen, d-C4 alkyl and C3-C4 cycloalkyi, in which the alkyl and cycloalkyi groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, C C3 alkoxy and C C3 alkylthio; or
R3 and R4 together with the carbon atom to which they are attached represent C=0, C=NORa, or C3-C6 cycloalkyi (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of a halogen, C C3 alkyl, C C3 alkoxy and C C3 alkylthio).
9. A compound according to any one of claims 1 , 2, 3, 4, 5, 6, 7, or 8 wherein each R5 independently represents halogen, cyano, C C4 alkyl, C3-C4 cycloalkyi, C C3 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C C3 alkylthio, -C(=NORa)Ci-C6alkyl, phenyl, heteroraryl (wherein heteroaryl is pyridyl, thiazolyl or oxazolyl), in which the alkyl, cycloalkyi, alkoxy, alkenyloxy, alkynyloxy, phenyl and heteroaryl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, Ci-C3 alkyl and C C3 alkoxy; n is 0, 1 or 2.
A compound according to any one of claims 1 , 2, 3, 4, 5, 6, 7, 8, or 9 wherein R6 is hydrogen or C C3 alkyl. A compound according to claim 1 wherein R-i and R2 are each independently selected from hydrogen and CrC4 alkyl, in which the alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, methoxy and methylthio; or
Ri and R2 together with the carbon atom to which they are attached represent a C3-C4 cycloalkyi group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen and Ci-C3 alkyl);
R3 and R4 are each independently selected from hydrogen, halogen and C C4 alkyl, in which the alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, methoxy and methylthio; or
R3 and R4 together with the carbon atom to which they are attached represent C=0,
C=NORa or C3-C4 cycloalkyi (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of a halogen and C C3 alkyl);
each R5 independently represents halogen, cyano, C C4 alkyl, C3-C4 cycloalkyi or phenyl, in which the alkyl, cycloalkyi and phenyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen or C C3 alkyl; n is 0, 1 or 2;
R6 is hydrogen or methyl;
each R7 independently represents cyano, halogen, C C4 alkyl, C C4 haloalkyl, C2-C3 alkynyl, C C4 alkylthio or C3-C4 cycloalkyi; m is 0, 1 or 2; and
Ra is selected from hydrogen and C C4 alkyl, in which the alkyl group may be optionally substituted with 1 to 3 halogen atoms;
or a salt or N-oxide thereof.
A compound according to claim 1 wherein R-i and R2 are each independently selected from hydrogen and C C3 alkyl; or
Ri and R2 together with the carbon atom to which they are attached represent a C3-C4 cycloalkyi group;
R3 and R4 are each independently selected from hydrogen, fluoro or C C3 alkyl; or R3 and R4 together with the carbon atom to which they are attached represent C=0 or C3-C4 cycloalkyi;
each R5 independently represents halogen, C C3 alkyl or C3-C4 cycloalkyi, in which the alkyl and cycloalkyi groups may be optionally substituted with 1 to 3 fluoro atoms; n is 0, 1 or 2;
R6 is hydrogen; and
each R7 independently represents fluoro, chloro or C C3 alkyl; m is 1 or 2; or a salt or N-oxide thereof.
A composition comprising a fungicidally effective amount of a compound of formula (I) as defined in any of claims 1 - 12.
A composition according to claim 13, wherein the composition further comprises at least one additional active ingredient and/or a diluent.
A method of combating, preventing or controlling phytopathogenic microorganisms which comprises applying to a phytopathogen, to the locus of a phytopathogen, or to a plant susceptible to attack by a phytopathogen, or to propagation material thereof, a fungicidally effective amount of a compound of formula (I) as defined in any of claims 1 - 12 or a composition comprising a fungicidally effective amount of a compound of formula (I) as defined in any of claims 1 - 12.
PCT/EP2016/056127 2015-03-27 2016-03-21 Microbiocidal heterobicyclic derivatives WO2016156085A1 (en)

Priority Applications (21)

Application Number Priority Date Filing Date Title
JP2017550509A JP6662901B2 (en) 2015-03-27 2016-03-21 Microbicidal bicyclic heterocyclic derivatives
MA40816A MA40816A1 (en) 2015-03-27 2016-03-21 Heterobicyclic Microbiocidal Derivatives
EA201792145A EA033690B1 (en) 2015-03-27 2016-03-21 Microbiocidal heterobicyclic derivatives
KR1020177026411A KR102565369B1 (en) 2015-03-27 2016-03-21 Microbial heterobicyclic derivatives
PL16711262T PL3274343T3 (en) 2015-03-27 2016-03-21 Microbiocidal heterobicyclic derivatives
AU2016239625A AU2016239625B2 (en) 2015-03-27 2016-03-21 Microbiocidal heterobicyclic derivatives
CN201680018352.7A CN107428722B (en) 2015-03-27 2016-03-21 Microbicidal heterobicyclic derivatives
CN202010122236.8A CN111303116B (en) 2015-03-27 2016-03-21 Microbiocidal heterobicyclic derivatives
TNP/2017/000407A TN2017000407A1 (en) 2015-03-27 2016-03-21 Microbiocidal heterobicyclic derivatives.
US15/561,788 US10273221B2 (en) 2015-03-27 2016-03-21 Microbiocidal heterobicyclic derivatives
EP20159778.8A EP3683213B1 (en) 2015-03-27 2016-03-21 Intermediate for the preparation of microbiocidal heterobicyclic derivatives
ES16711262T ES2791193T3 (en) 2015-03-27 2016-03-21 Microbicidal heterobicyclic derivatives
EP21158139.2A EP3848364A1 (en) 2015-03-27 2016-03-21 Microbiocidal heterobicyclic derivatives and intermediates for their preparation
EP16711262.2A EP3274343B1 (en) 2015-03-27 2016-03-21 Microbiocidal heterobicyclic derivatives
CR20170418A CR20170418A (en) 2015-03-27 2016-03-21 MICROBICIDE HETEROBICYCLIC DERIVATIVES
BR112017020349-9A BR112017020349B1 (en) 2015-03-27 2016-03-21 HETEROBICYCLIC MICROBICIDES DERIVATIVES
CA2978996A CA2978996A1 (en) 2015-03-27 2016-03-21 Microbiocidal benzimidazolyl-isoquinoline heterobicyclic derivatives
UAA201710269A UA120960C2 (en) 2015-03-27 2016-03-21 Microbiocidal heterobicyclic derivatives
MX2017012195A MX2017012195A (en) 2015-03-27 2016-03-21 Microbiocidal heterobicyclic derivatives.
IL254190A IL254190B (en) 2015-03-27 2017-08-28 Microbiocidal heterobicyclic derivatives
CONC2017/0009652A CO2017009652A2 (en) 2015-03-27 2017-09-22 Heterobicicyclic Microbicide Derivatives

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP15161494 2015-03-27
EP15161494.8 2015-03-27

Publications (1)

Publication Number Publication Date
WO2016156085A1 true WO2016156085A1 (en) 2016-10-06

Family

ID=53058973

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2016/056127 WO2016156085A1 (en) 2015-03-27 2016-03-21 Microbiocidal heterobicyclic derivatives

Country Status (24)

Country Link
US (1) US10273221B2 (en)
EP (3) EP3683213B1 (en)
JP (1) JP6662901B2 (en)
KR (1) KR102565369B1 (en)
CN (3) CN111892576A (en)
AR (1) AR104046A1 (en)
AU (1) AU2016239625B2 (en)
BR (1) BR112017020349B1 (en)
CA (1) CA2978996A1 (en)
CL (1) CL2017002426A1 (en)
CO (1) CO2017009652A2 (en)
CR (1) CR20170418A (en)
EA (1) EA033690B1 (en)
ES (2) ES2791193T3 (en)
GE (1) GEP20197032B (en)
HU (1) HUE049090T2 (en)
IL (1) IL254190B (en)
MA (1) MA40816A1 (en)
MX (1) MX2017012195A (en)
PL (1) PL3274343T3 (en)
PT (1) PT3274343T (en)
TN (1) TN2017000407A1 (en)
UA (1) UA120960C2 (en)
WO (1) WO2016156085A1 (en)

Cited By (132)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017025510A1 (en) * 2015-08-12 2017-02-16 Syngenta Participations Ag Microbiocidal heterobicyclic derivatives
WO2018060039A1 (en) * 2016-09-28 2018-04-05 Syngenta Participations Ag Fungicidal compositions
WO2018073110A1 (en) 2016-10-20 2018-04-26 Basf Se Quinoline compounds as fungicides
WO2018116072A1 (en) * 2016-12-20 2018-06-28 Pi Industries Ltd. Heterocyclic compounds
WO2018134127A1 (en) 2017-01-23 2018-07-26 Basf Se Fungicidal pyridine compounds
WO2018149851A1 (en) 2017-02-16 2018-08-23 Syngenta Participations Ag Fungicidal compositions
WO2018184882A1 (en) 2017-04-06 2018-10-11 Basf Se Pyridine compounds
WO2018206419A1 (en) 2017-05-12 2018-11-15 Syngenta Participations Ag Microbiocidal heterobicyclic derivatives
WO2019101580A1 (en) 2017-11-21 2019-05-31 Syngenta Participations Ag Fungicidal compositions
WO2020165403A1 (en) 2019-02-15 2020-08-20 Syngenta Crop Protection Ag Phenyl substituted thiazole derivatives as microbiocidal compounds
WO2020182649A1 (en) 2019-03-08 2020-09-17 Syngenta Crop Protection Ag Pesticidally active azole-amide compounds
WO2020188014A1 (en) 2019-03-20 2020-09-24 Syngenta Crop Protection Ag Pesticidally active azole amide compounds
WO2020188027A1 (en) 2019-03-20 2020-09-24 Syngenta Crop Protection Ag Pesticidally active azole amide compounds
WO2020193341A1 (en) 2019-03-22 2020-10-01 Syngenta Crop Protection Ag N-[1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-2-cyclopropyl-6-(trifluoromethyl)pyridine-4-carboxamide derivatives and related compounds as insecticides
WO2020193387A1 (en) 2019-03-22 2020-10-01 Syngenta Crop Protection Ag Fungicidal compounds
WO2020193618A1 (en) 2019-03-27 2020-10-01 Syngenta Crop Protection Ag Microbiocidal thiazole derivatives
WO2020201079A1 (en) 2019-03-29 2020-10-08 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2020201398A1 (en) 2019-04-05 2020-10-08 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2020208095A1 (en) 2019-04-10 2020-10-15 Syngenta Crop Protection Ag Microbiocidal picolinamide derivatives
WO2020208036A1 (en) 2019-04-11 2020-10-15 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2020208096A1 (en) 2019-04-10 2020-10-15 Syngenta Crop Protection Ag Fungicidal compositions
WO2020239853A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2020239854A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2020239856A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2020239855A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2021004968A1 (en) 2019-07-05 2021-01-14 Syngenta Crop Protection Ag Microbiocidal picolinamide derivatives
WO2021009026A1 (en) 2019-07-12 2021-01-21 Syngenta Crop Protection Ag Methyl 2-[(4-methoxyimino-tetralin-6-yl]prop-2-enoate derivatives, chromane, isochromane, 6,7,8,9-tetrahydrobenzo[7]annulene, 1h-isobenzofurane and indane analogues thereof, and similar compounds, as agrochemical fungicides
WO2021037614A1 (en) 2019-08-23 2021-03-04 Syngenta Crop Protection Ag Pesticidally active pyrazine-amide compounds
WO2021043616A1 (en) 2019-09-02 2021-03-11 Syngenta Crop Protection Ag Strigolactone derivatives as plant growth regulator compounds
WO2021053110A1 (en) 2019-09-20 2021-03-25 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur and sulfoximine containing substituents
WO2021053161A1 (en) 2019-09-20 2021-03-25 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2021083936A1 (en) 2019-11-01 2021-05-06 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2021110891A1 (en) 2019-12-04 2021-06-10 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic amino compounds
WO2021122645A1 (en) 2019-12-20 2021-06-24 Syngenta Crop Protection Ag Pesticidally active azole-amide compounds
WO2021136722A1 (en) 2019-12-31 2021-07-08 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021140122A1 (en) 2020-01-06 2021-07-15 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021148639A1 (en) 2020-01-24 2021-07-29 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2021151926A1 (en) 2020-01-30 2021-08-05 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic amino compounds
WO2021160680A1 (en) 2020-02-11 2021-08-19 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2021170881A1 (en) 2020-02-27 2021-09-02 Syngenta Crop Protection Ag Pesticidally active diazine-bisamide compounds
WO2021175822A1 (en) 2020-03-02 2021-09-10 Syngenta Crop Protection Ag Pesticidally amidine-substituted benzoic acid amide compounds
WO2021176007A1 (en) 2020-03-05 2021-09-10 Syngenta Crop Protection Ag Fungicidal compositions
WO2021176057A1 (en) 2020-03-05 2021-09-10 Syngenta Crop Protection Ag Fungicidal compositions
WO2021180596A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021180592A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021180598A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021204822A1 (en) 2020-04-08 2021-10-14 Syngenta Crop Protection Ag Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives
WO2021204857A1 (en) 2020-04-08 2021-10-14 Syngenta Crop Protection Ag Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives
WO2021204855A1 (en) 2020-04-08 2021-10-14 Syngenta Crop Protection Ag Microbiocidal quinoline dihydropyrrolopyrazine derivatives
WO2021213929A1 (en) 2020-04-20 2021-10-28 Syngenta Crop Protection Ag Pesticidally active substituted 1,3-dihydro-2h-imidazo[4,5-c]pyridin-2-one derivatives with sulfur containing substituents
WO2021219810A1 (en) 2020-04-30 2021-11-04 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021219778A1 (en) 2020-04-30 2021-11-04 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021219775A1 (en) 2020-04-30 2021-11-04 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021219780A1 (en) 2020-05-01 2021-11-04 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021224409A1 (en) 2020-05-06 2021-11-11 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021224102A1 (en) 2020-05-05 2021-11-11 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021244950A1 (en) 2020-06-03 2021-12-09 Syngenta Crop Protection Ag Fungicidal compositions
WO2021244952A1 (en) 2020-06-03 2021-12-09 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2021244951A1 (en) 2020-06-03 2021-12-09 Syngenta Crop Protection Ag Fungicidal compositions
WO2022013417A1 (en) 2020-07-17 2022-01-20 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022017975A1 (en) 2020-07-18 2022-01-27 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022043576A2 (en) 2020-08-31 2022-03-03 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022049141A1 (en) 2020-09-01 2022-03-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022049144A1 (en) 2020-09-02 2022-03-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022049146A1 (en) 2020-09-02 2022-03-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022048988A1 (en) 2020-09-02 2022-03-10 Syngenta Participations Ag Plant growth regulator compounds
WO2022053567A1 (en) 2020-09-09 2022-03-17 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022058580A1 (en) 2020-09-21 2022-03-24 Syngenta Crop Protection Ag Microbiocidal compounds
WO2022084346A1 (en) 2020-10-22 2022-04-28 Syngenta Crop Protection Ag Zealactone derivatives as plant growth regulators
WO2022101265A1 (en) 2020-11-13 2022-05-19 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2022157334A1 (en) 2021-01-21 2022-07-28 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022157122A1 (en) 2021-01-22 2022-07-28 Syngenta Crop Protection Ag Method for the control or suppression of phytopathogenic bacteria
WO2022157188A2 (en) 2021-01-23 2022-07-28 Syngenta Crop Protection Ag Pesticidally active heteroaromatic compounds
WO2022207462A1 (en) 2021-03-30 2022-10-06 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2022207665A1 (en) 2021-03-31 2022-10-06 Syngenta Crop Protection Ag Microbiocidal quinoline/quinoxaline benzothiazine derivatives
WO2022207479A1 (en) 2021-03-27 2022-10-06 Syngenta Crop Protection Ag Microbiocidal isonicotinic amide derivatives
WO2022219146A2 (en) 2021-04-16 2022-10-20 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2022223376A1 (en) 2021-04-20 2022-10-27 Syngenta Crop Protection Ag Microbiocidal quinoline/quinoxaline isoquinoline derivatives
WO2022233869A1 (en) 2021-05-04 2022-11-10 Syngenta Crop Protection Ag Use of clethodim for insect control
WO2022253645A1 (en) 2021-06-01 2022-12-08 Syngenta Crop Protection Ag Microbiocidal tetrahydroisoquinoline derivatives
WO2022253841A1 (en) 2021-06-02 2022-12-08 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfoximine containing substituents
WO2022258481A1 (en) 2021-06-09 2022-12-15 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2022268648A1 (en) 2021-06-24 2022-12-29 Syngenta Crop Protection Ag 2-[3-[1 [(quinazolin-4-yl)amino]ethyl]pyrazin-2-yl]thiazole-5-carbonitrile derivatives and similar compounds as pesticides
WO2023275116A1 (en) 2021-07-02 2023-01-05 Syngenta Crop Protection Ag Use of fluazifop-p-butyl for insect control
WO2023006634A1 (en) 2021-07-27 2023-02-02 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023006789A1 (en) 2021-07-29 2023-02-02 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2023012044A1 (en) 2021-08-02 2023-02-09 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2023012081A1 (en) 2021-08-05 2023-02-09 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023017094A1 (en) 2021-08-10 2023-02-16 Syngenta Crop Protection Ag 2,2-difluoro-5h-[1,3]dioxolo[4,5-f]isoindol-7-one derivatives as pesticides
WO2023017016A1 (en) 2021-08-10 2023-02-16 Syngenta Crop Protection Ag Fungicide mixture
WO2023021020A1 (en) 2021-08-19 2023-02-23 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023061838A1 (en) 2021-10-14 2023-04-20 Syngenta Crop Protection Ag Imidazo[1,2-a]pyridine derivatives
WO2023072945A1 (en) 2021-10-25 2023-05-04 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023072785A1 (en) 2021-10-29 2023-05-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2023072849A1 (en) 2021-10-27 2023-05-04 Syngenta Crop Protection Ag Pesticidally active pyridazinone compounds
WO2023072784A1 (en) 2021-10-29 2023-05-04 Syngenta Crop Protection Ag Fungicidal compositions comprising fludioxonil
WO2023089049A2 (en) 2021-11-19 2023-05-25 Syngenta Crop Protection Ag Microbiocidal isonicotinic amide derivatives
WO2023094303A1 (en) 2021-11-25 2023-06-01 Syngenta Crop Protection Ag Microbiocidal heterobiaryl amide derivatives
WO2023094304A1 (en) 2021-11-25 2023-06-01 Syngenta Crop Protection Ag Microbiocidal heterobiaryl amide derivatives
WO2023099460A1 (en) 2021-12-02 2023-06-08 Syngenta Crop Protection Ag Fungicidal compositions
WO2023104714A1 (en) 2021-12-10 2023-06-15 Syngenta Crop Protection Ag Pesticidally active pyridazinone compounds
EP4197333A1 (en) 2021-12-15 2023-06-21 Syngenta Crop Protection AG Method for controlling diamide resistant pests & compounds therefor
WO2023111215A1 (en) 2021-12-17 2023-06-22 Syngenta Crop Protection Ag Microbiocidal pyridine-substituted benzothiazine derivatives
WO2023110871A1 (en) 2021-12-17 2023-06-22 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2023110710A1 (en) 2021-12-13 2023-06-22 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023110928A1 (en) 2021-12-17 2023-06-22 Syngenta Crop Protection Ag Fungicidal compositions
WO2023110869A1 (en) 2021-12-15 2023-06-22 Syngenta Crop Protection Ag Microbiocidal bicycle heterocyclic derivatives
WO2023118434A1 (en) 2021-12-22 2023-06-29 Globachem Nv Pesticidally active amide compounds
WO2023118011A1 (en) 2021-12-22 2023-06-29 Syngenta Crop Protection Ag Microbiocidal aza-heterobiaryl derivatives
WO2023117625A1 (en) 2021-12-22 2023-06-29 Syngenta Crop Protection Ag Fungicidal compositions
WO2023139166A1 (en) 2022-01-19 2023-07-27 Syngenta Crop Protection Ag Methods for controlling plant pathogens
WO2023148206A1 (en) 2022-02-02 2023-08-10 Syngenta Crop Protection Ag Microbiocidal n-amide derivatives
WO2023148368A1 (en) 2022-02-07 2023-08-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023148369A1 (en) 2022-02-07 2023-08-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023166067A1 (en) 2022-03-02 2023-09-07 Syngenta Crop Protection Ag Microbiocidal pyridazinone amide derivatives
WO2023187191A1 (en) 2022-04-01 2023-10-05 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023209238A1 (en) 2022-04-29 2023-11-02 Syngenta Crop Protection Ag Fungicidal compositions
WO2023217989A1 (en) 2022-05-12 2023-11-16 Syngenta Crop Protection Ag Alkoxy heteroaryl- carboxamide or thioamide compounds
WO2023247552A1 (en) 2022-06-21 2023-12-28 Syngenta Crop Protection Ag Microbiocidal bicyclic heterocyclic carboxamide derivatives
WO2023247360A1 (en) 2022-06-21 2023-12-28 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2024008567A1 (en) 2022-07-07 2024-01-11 Syngenta Crop Protection Ag Precision application devices and compositions
WO2024018016A1 (en) 2022-07-21 2024-01-25 Syngenta Crop Protection Ag Crystalline forms of 1,2,4-oxadiazole fungicides
WO2024017788A1 (en) 2022-07-22 2024-01-25 Syngenta Crop Protection Ag Solid form of a heterocyclic amide derivative
WO2024022910A1 (en) 2022-07-26 2024-02-01 Syngenta Crop Protection Ag 1-[1-[2-(pyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-3-[2,4-dichloro-5-phenyl]urea derivatives and similar compounds as pesticides
WO2024033374A1 (en) 2022-08-11 2024-02-15 Syngenta Crop Protection Ag Novel arylcarboxamide or arylthioamide compounds
WO2024038053A1 (en) 2022-08-16 2024-02-22 Syngenta Crop Protection Ag New use of pydiflumetofen
WO2024056732A1 (en) 2022-09-16 2024-03-21 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2024068950A1 (en) 2022-09-30 2024-04-04 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2024068655A1 (en) 2022-09-28 2024-04-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2024068838A1 (en) 2022-09-28 2024-04-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2024068656A1 (en) 2022-09-28 2024-04-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2024068947A1 (en) 2022-09-30 2024-04-04 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090325998A1 (en) * 2006-12-01 2009-12-31 Hiroyuki Ito Soil treating agent or seed treating agent comprising quinoline compounds or salts thereof as active ingredient,or method for preventing plant diseases by using the same
EP2223919A1 (en) * 2007-12-26 2010-09-01 Nippon Soda Co., Ltd. Nitrogen-containing heterocyclic compound and bactericide for agricultural and horticultural use
US20120282349A1 (en) * 2009-12-22 2012-11-08 Mitsui Chemicals Agro, Inc. Plant disease control composition and method for controlling plant disease by applying the same

Family Cites Families (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2538341A (en) * 1949-09-20 1951-01-16 Smith Kline French Lab Method for producing 1-hydroxyisoquinolines
SU449052A1 (en) * 1972-01-10 1974-11-05 Латвийский Филиал Всесоюзного Ордена Трудового Красного Знамени Научно-Исследовательского Института Химических Реактивов И Особо Чистых Химических Веществ Method for preparing 2-p-1,4-dioxo-3-substituted-1,2,3,4-tetrahydroisoquinolines
JPS61107392A (en) 1984-10-31 1986-05-26 株式会社東芝 Image processing system
BR8600161A (en) 1985-01-18 1986-09-23 Plant Genetic Systems Nv CHEMICAL GENE, HYBRID, INTERMEDIATE PLASMIDIO VECTORS, PROCESS TO CONTROL INSECTS IN AGRICULTURE OR HORTICULTURE, INSECTICIDE COMPOSITION, PROCESS TO TRANSFORM PLANT CELLS TO EXPRESS A PLANTINIDE TOXIN, PRODUCED BY CULTURES, UNITED BY BACILLA
GB8726735D0 (en) * 1987-11-14 1987-12-16 Wellcome Found Pesticidal compounds
CA1340685C (en) 1988-07-29 1999-07-27 Frederick Meins Dna sequences encoding polypeptides having beta-1,3-glucanase activity
AU613521B2 (en) 1988-09-02 1991-08-01 Sankyo Company Limited 13-substituted milbemycin derivatives, their preparation and use
US5169629A (en) 1988-11-01 1992-12-08 Mycogen Corporation Process of controlling lepidopteran pests, using bacillus thuringiensis isolate denoted b.t ps81gg
NZ231804A (en) 1988-12-19 1993-03-26 Ciba Geigy Ag Insecticidal toxin from leiurus quinquestriatus hebraeus
US5015630A (en) 1989-01-19 1991-05-14 Merck & Co., Inc. 5-oxime avermectin derivatives
NO176766C (en) 1989-02-07 1995-05-24 Meiji Seika Kaisha Process for the preparation of a compound having anthelmintic activity
ATE241699T1 (en) 1989-03-24 2003-06-15 Syngenta Participations Ag DISEASE RESISTANT TRANSGENIC PLANT
GB8910624D0 (en) 1989-05-09 1989-06-21 Ici Plc Bacterial strains
CA2015951A1 (en) 1989-05-18 1990-11-18 Mycogen Corporation Novel bacillus thuringiensis isolates active against lepidopteran pests, and genes encoding novel lepidopteran-active toxins
DE69018772T2 (en) 1989-11-07 1996-03-14 Pioneer Hi Bred Int Larvae kill lectins and plant resistance to insects based on them.
JPH085894B2 (en) 1990-03-01 1996-01-24 三共株式会社 Milbemycin ether derivative
DE4025891A1 (en) 1990-08-16 1992-02-20 Bayer Ag PYRIMIDYL-SUBSTITUTED ACRYLIC ACID ESTERS
US5639949A (en) 1990-08-20 1997-06-17 Ciba-Geigy Corporation Genes for the synthesis of antipathogenic substances
JPH0570366A (en) 1991-03-08 1993-03-23 Meiji Seika Kaisha Ltd Composition for medicine
UA48104C2 (en) 1991-10-04 2002-08-15 Новартіс Аг Dna fragment including sequence that codes an insecticide protein with optimization for corn, dna fragment providing directed preferable for the stem core expression of the structural gene of the plant related to it, dna fragment providing specific for the pollen expression of related to it structural gene in the plant, recombinant dna molecule, method for obtaining a coding sequence of the insecticide protein optimized for corn, method of corn plants protection at least against one pest insect
EP0634408B1 (en) 1992-03-17 2002-01-02 Fujisawa Pharmaceutical Co., Ltd. Depsipeptide derivative, production thereof and use thereof
ES2118816T3 (en) 1992-04-28 1998-10-01 Yashima Kagaku Kogyo Kk 2- (2,6-DIFLUOROFENIL) -4- (2-ETOXI-4-TERC-BUTILFENIL) -2-OXAZOLINA.
DE4317458A1 (en) 1992-06-11 1993-12-16 Bayer Ag Use of cyclic depsipeptides with 18 ring atoms for the control of endoparasites, new cyclic depsipeptides with 18 ring atoms and process for their preparation
CA2105251C (en) 1992-09-01 2004-12-07 Mitsugi Shibano Novel processes for the production of 13-ether derivatives of milbemycins, and novel intermediates therefor
GB9300883D0 (en) 1993-01-18 1993-03-10 Pfizer Ltd Antiparasitic agents
CN1073560C (en) 1993-02-19 2001-10-24 明治制果株式会社 PF1022 derivative, cyclic depsipeptide
DE4317457A1 (en) 1993-05-26 1994-12-01 Bayer Ag Octacyclodepsipeptides with endoparasiticidal activity
EP0739344B1 (en) 1994-01-14 1998-11-11 Pfizer Inc. Antiparasitic pyrrolobenzoxazine compounds
GB9402916D0 (en) 1994-02-16 1994-04-06 Pfizer Ltd Antiparasitic agents
US5530195A (en) 1994-06-10 1996-06-25 Ciba-Geigy Corporation Bacillus thuringiensis gene encoding a toxin active against insects
DE4437198A1 (en) 1994-10-18 1996-04-25 Bayer Ag Process for sulfonylation, sulfenylation and phosphorylation of cyclic depsipeptides
DE4440193A1 (en) 1994-11-10 1996-05-15 Bayer Ag Use of dioxomorpholines to control endoparasites, new dioxomorpholines and processes for their production
DE19520936A1 (en) 1995-06-08 1996-12-12 Bayer Ag Ectoparasiticides means
KR100482919B1 (en) 1996-03-11 2005-10-12 신젠타 파티서페이션즈 아게 Pyrimidine-4-one derivatives as insecticides
RU2272030C2 (en) * 2000-08-01 2006-03-20 Оно Фармасьютикал Ко., Лтд. Derivatives of 3,4-dihydroisoquinoline and pharmaceutical agent comprising its as active component
WO2002015701A2 (en) 2000-08-25 2002-02-28 Syngenta Participations Ag Bacillus thuringiensis crystal protein hybrids
US7230167B2 (en) 2001-08-31 2007-06-12 Syngenta Participations Ag Modified Cry3A toxins and nucleic acid sequences coding therefor
WO2003052073A2 (en) 2001-12-17 2003-06-26 Syngenta Participations Ag Novel corn event
WO2003064389A1 (en) * 2002-01-31 2003-08-07 Ono Pharmaceutical Co., Ltd. Nitrogen-containing bicyclic compounds and drugs containing the same as the active ingredient
CN1625336A (en) 2002-04-04 2005-06-08 瓦伦特生物科学公司 Enhanced herbicide composition
GB0303439D0 (en) 2003-02-14 2003-03-19 Pfizer Ltd Antiparasitic terpene alkaloids
JP4939057B2 (en) 2004-01-23 2012-05-23 三井化学アグロ株式会社 3- (Dihydro (tetrahydro) isoquinolin-1-yl) quinoline compounds
DE102005007160A1 (en) 2005-02-16 2006-08-24 Basf Ag Pyrazolecarboxylic acid anilides, process for their preparation and compositions containing them for controlling harmful fungi
EP1940813B1 (en) 2005-10-25 2010-11-24 Syngenta Participations AG Heterocyclic amide derivatives useful as microbiocides
ATE438643T1 (en) 2006-02-16 2009-08-15 Syngenta Participations Ag PESTICIDES CONTAINING A BICYCLIC BISAMIDE STRUCTURE
TWI528899B (en) 2010-12-29 2016-04-11 杜邦股份有限公司 Mesoionic pesticides
WO2013004652A1 (en) * 2011-07-04 2013-01-10 Bayer Intellectual Property Gmbh Use of substituted isoquinolinones, isoquinolindiones, isoquinolintriones and dihydroisoquinolinones or in each case salts thereof as active agents against abiotic stress in plants
RU2616608C2 (en) 2011-09-29 2017-04-18 Мицуи Кемикалз Агро, Инк. Method of producing derivatives of 4,4-difluoro-3,4-dihydroisoquinolin
WO2013156433A1 (en) 2012-04-17 2013-10-24 Syngenta Participations Ag Insecticidally active thiazole derivatives
WO2013156431A1 (en) 2012-04-17 2013-10-24 Syngenta Participations Ag Pesticidally active pyridyl- and pyrimidyl- substituted thiazole and thiadiazole derivatives
UA111305C2 (en) * 2012-12-21 2016-04-11 Пфайзер Інк. Condensed with lactams of aryl and heteroaryl
EP2978762A1 (en) * 2013-03-27 2016-02-03 Bristol-Myers Squibb Company Piperazine and homopiperazine derivatives as hiv attachment inhibitors
EP3114127B1 (en) 2014-03-04 2017-11-29 Syngenta Participations AG Microbiocidal heterobicyclic derivatives

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090325998A1 (en) * 2006-12-01 2009-12-31 Hiroyuki Ito Soil treating agent or seed treating agent comprising quinoline compounds or salts thereof as active ingredient,or method for preventing plant diseases by using the same
EP2223919A1 (en) * 2007-12-26 2010-09-01 Nippon Soda Co., Ltd. Nitrogen-containing heterocyclic compound and bactericide for agricultural and horticultural use
US20120282349A1 (en) * 2009-12-22 2012-11-08 Mitsui Chemicals Agro, Inc. Plant disease control composition and method for controlling plant disease by applying the same

Cited By (143)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EA035584B1 (en) * 2015-08-12 2020-07-10 Зингента Партисипейшнс Аг Microbiocidal heterobicyclic derivatives
AU2016305250B2 (en) * 2015-08-12 2020-10-22 Syngenta Participations Ag Microbiocidal heterobicyclic derivatives
EP3929197A1 (en) * 2015-08-12 2021-12-29 Syngenta Participations Ag Intermediates for the synthesis of microbiocidal heterobicyclic derivatives
WO2017025510A1 (en) * 2015-08-12 2017-02-16 Syngenta Participations Ag Microbiocidal heterobicyclic derivatives
US10906897B2 (en) 2015-08-12 2021-02-02 Syngenta Participations Ag Microbiocidal heterobicyclic derivatives
JP7149934B2 (en) 2016-09-28 2022-10-07 シンジェンタ パーティシペーションズ アーゲー Bactericidal and fungicidal composition
JP2019532060A (en) * 2016-09-28 2019-11-07 シンジェンタ パーティシペーションズ アーゲー Bactericidal and fungicidal composition
WO2018060039A1 (en) * 2016-09-28 2018-04-05 Syngenta Participations Ag Fungicidal compositions
US10966425B2 (en) 2016-09-28 2021-04-06 Syngenta Participations Ag Fungicidal compositions
WO2018073110A1 (en) 2016-10-20 2018-04-26 Basf Se Quinoline compounds as fungicides
WO2018116072A1 (en) * 2016-12-20 2018-06-28 Pi Industries Ltd. Heterocyclic compounds
WO2018134127A1 (en) 2017-01-23 2018-07-26 Basf Se Fungicidal pyridine compounds
US11124508B2 (en) 2017-02-16 2021-09-21 Syngenta Participations Ag Fungicidal compositions
JP2020507617A (en) * 2017-02-16 2020-03-12 シンジェンタ パーティシペーションズ アーゲー Bactericidal / fungicidal composition
JP7076460B2 (en) 2017-02-16 2022-05-27 シンジェンタ パーティシペーションズ アーゲー Bactericidal and fungal killing composition
WO2018149851A1 (en) 2017-02-16 2018-08-23 Syngenta Participations Ag Fungicidal compositions
CN110300521A (en) * 2017-02-16 2019-10-01 先正达参股股份有限公司 Fungicidal composition
WO2018184882A1 (en) 2017-04-06 2018-10-11 Basf Se Pyridine compounds
WO2018206419A1 (en) 2017-05-12 2018-11-15 Syngenta Participations Ag Microbiocidal heterobicyclic derivatives
WO2019101580A1 (en) 2017-11-21 2019-05-31 Syngenta Participations Ag Fungicidal compositions
WO2020165403A1 (en) 2019-02-15 2020-08-20 Syngenta Crop Protection Ag Phenyl substituted thiazole derivatives as microbiocidal compounds
WO2020182649A1 (en) 2019-03-08 2020-09-17 Syngenta Crop Protection Ag Pesticidally active azole-amide compounds
WO2020188027A1 (en) 2019-03-20 2020-09-24 Syngenta Crop Protection Ag Pesticidally active azole amide compounds
WO2020188014A1 (en) 2019-03-20 2020-09-24 Syngenta Crop Protection Ag Pesticidally active azole amide compounds
WO2020193387A1 (en) 2019-03-22 2020-10-01 Syngenta Crop Protection Ag Fungicidal compounds
WO2020193341A1 (en) 2019-03-22 2020-10-01 Syngenta Crop Protection Ag N-[1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-2-cyclopropyl-6-(trifluoromethyl)pyridine-4-carboxamide derivatives and related compounds as insecticides
WO2020193618A1 (en) 2019-03-27 2020-10-01 Syngenta Crop Protection Ag Microbiocidal thiazole derivatives
WO2020201079A1 (en) 2019-03-29 2020-10-08 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2020201398A1 (en) 2019-04-05 2020-10-08 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2020208096A1 (en) 2019-04-10 2020-10-15 Syngenta Crop Protection Ag Fungicidal compositions
WO2020208095A1 (en) 2019-04-10 2020-10-15 Syngenta Crop Protection Ag Microbiocidal picolinamide derivatives
WO2020208036A1 (en) 2019-04-11 2020-10-15 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2020239856A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2020239855A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2020239854A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2020239853A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2021004968A1 (en) 2019-07-05 2021-01-14 Syngenta Crop Protection Ag Microbiocidal picolinamide derivatives
WO2021009026A1 (en) 2019-07-12 2021-01-21 Syngenta Crop Protection Ag Methyl 2-[(4-methoxyimino-tetralin-6-yl]prop-2-enoate derivatives, chromane, isochromane, 6,7,8,9-tetrahydrobenzo[7]annulene, 1h-isobenzofurane and indane analogues thereof, and similar compounds, as agrochemical fungicides
WO2021037614A1 (en) 2019-08-23 2021-03-04 Syngenta Crop Protection Ag Pesticidally active pyrazine-amide compounds
WO2021043616A1 (en) 2019-09-02 2021-03-11 Syngenta Crop Protection Ag Strigolactone derivatives as plant growth regulator compounds
WO2021053110A1 (en) 2019-09-20 2021-03-25 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur and sulfoximine containing substituents
WO2021053161A1 (en) 2019-09-20 2021-03-25 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2021083936A1 (en) 2019-11-01 2021-05-06 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2021110891A1 (en) 2019-12-04 2021-06-10 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic amino compounds
WO2021122645A1 (en) 2019-12-20 2021-06-24 Syngenta Crop Protection Ag Pesticidally active azole-amide compounds
WO2021136722A1 (en) 2019-12-31 2021-07-08 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021140122A1 (en) 2020-01-06 2021-07-15 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021148639A1 (en) 2020-01-24 2021-07-29 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2021151926A1 (en) 2020-01-30 2021-08-05 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic amino compounds
WO2021160680A1 (en) 2020-02-11 2021-08-19 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2021170881A1 (en) 2020-02-27 2021-09-02 Syngenta Crop Protection Ag Pesticidally active diazine-bisamide compounds
WO2021175822A1 (en) 2020-03-02 2021-09-10 Syngenta Crop Protection Ag Pesticidally amidine-substituted benzoic acid amide compounds
WO2021176057A1 (en) 2020-03-05 2021-09-10 Syngenta Crop Protection Ag Fungicidal compositions
WO2021176007A1 (en) 2020-03-05 2021-09-10 Syngenta Crop Protection Ag Fungicidal compositions
WO2021180596A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021180592A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021180598A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021204857A1 (en) 2020-04-08 2021-10-14 Syngenta Crop Protection Ag Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives
WO2021204822A1 (en) 2020-04-08 2021-10-14 Syngenta Crop Protection Ag Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives
WO2021204855A1 (en) 2020-04-08 2021-10-14 Syngenta Crop Protection Ag Microbiocidal quinoline dihydropyrrolopyrazine derivatives
WO2021213929A1 (en) 2020-04-20 2021-10-28 Syngenta Crop Protection Ag Pesticidally active substituted 1,3-dihydro-2h-imidazo[4,5-c]pyridin-2-one derivatives with sulfur containing substituents
WO2021219778A1 (en) 2020-04-30 2021-11-04 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021219775A1 (en) 2020-04-30 2021-11-04 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021219810A1 (en) 2020-04-30 2021-11-04 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021219780A1 (en) 2020-05-01 2021-11-04 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021224102A1 (en) 2020-05-05 2021-11-11 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021224409A1 (en) 2020-05-06 2021-11-11 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021244952A1 (en) 2020-06-03 2021-12-09 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2021244951A1 (en) 2020-06-03 2021-12-09 Syngenta Crop Protection Ag Fungicidal compositions
WO2021244950A1 (en) 2020-06-03 2021-12-09 Syngenta Crop Protection Ag Fungicidal compositions
WO2022013417A1 (en) 2020-07-17 2022-01-20 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022017975A1 (en) 2020-07-18 2022-01-27 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022043576A2 (en) 2020-08-31 2022-03-03 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022049141A1 (en) 2020-09-01 2022-03-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022049146A1 (en) 2020-09-02 2022-03-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022048988A1 (en) 2020-09-02 2022-03-10 Syngenta Participations Ag Plant growth regulator compounds
WO2022049144A1 (en) 2020-09-02 2022-03-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022053567A1 (en) 2020-09-09 2022-03-17 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022058580A1 (en) 2020-09-21 2022-03-24 Syngenta Crop Protection Ag Microbiocidal compounds
WO2022084346A1 (en) 2020-10-22 2022-04-28 Syngenta Crop Protection Ag Zealactone derivatives as plant growth regulators
WO2022101265A1 (en) 2020-11-13 2022-05-19 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2022157334A1 (en) 2021-01-21 2022-07-28 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022157122A1 (en) 2021-01-22 2022-07-28 Syngenta Crop Protection Ag Method for the control or suppression of phytopathogenic bacteria
WO2022157188A2 (en) 2021-01-23 2022-07-28 Syngenta Crop Protection Ag Pesticidally active heteroaromatic compounds
WO2022207479A1 (en) 2021-03-27 2022-10-06 Syngenta Crop Protection Ag Microbiocidal isonicotinic amide derivatives
WO2022207462A1 (en) 2021-03-30 2022-10-06 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2022207665A1 (en) 2021-03-31 2022-10-06 Syngenta Crop Protection Ag Microbiocidal quinoline/quinoxaline benzothiazine derivatives
WO2022219146A2 (en) 2021-04-16 2022-10-20 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2022223376A1 (en) 2021-04-20 2022-10-27 Syngenta Crop Protection Ag Microbiocidal quinoline/quinoxaline isoquinoline derivatives
WO2022233869A1 (en) 2021-05-04 2022-11-10 Syngenta Crop Protection Ag Use of clethodim for insect control
WO2022253645A1 (en) 2021-06-01 2022-12-08 Syngenta Crop Protection Ag Microbiocidal tetrahydroisoquinoline derivatives
WO2022253841A1 (en) 2021-06-02 2022-12-08 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfoximine containing substituents
WO2022258481A1 (en) 2021-06-09 2022-12-15 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2022268648A1 (en) 2021-06-24 2022-12-29 Syngenta Crop Protection Ag 2-[3-[1 [(quinazolin-4-yl)amino]ethyl]pyrazin-2-yl]thiazole-5-carbonitrile derivatives and similar compounds as pesticides
WO2023275116A1 (en) 2021-07-02 2023-01-05 Syngenta Crop Protection Ag Use of fluazifop-p-butyl for insect control
WO2023006634A1 (en) 2021-07-27 2023-02-02 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023006789A1 (en) 2021-07-29 2023-02-02 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2023012044A1 (en) 2021-08-02 2023-02-09 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2023012081A1 (en) 2021-08-05 2023-02-09 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023017094A1 (en) 2021-08-10 2023-02-16 Syngenta Crop Protection Ag 2,2-difluoro-5h-[1,3]dioxolo[4,5-f]isoindol-7-one derivatives as pesticides
WO2023017016A1 (en) 2021-08-10 2023-02-16 Syngenta Crop Protection Ag Fungicide mixture
WO2023021020A1 (en) 2021-08-19 2023-02-23 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023061838A1 (en) 2021-10-14 2023-04-20 Syngenta Crop Protection Ag Imidazo[1,2-a]pyridine derivatives
WO2023072945A1 (en) 2021-10-25 2023-05-04 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023072849A1 (en) 2021-10-27 2023-05-04 Syngenta Crop Protection Ag Pesticidally active pyridazinone compounds
WO2023072785A1 (en) 2021-10-29 2023-05-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2023072784A1 (en) 2021-10-29 2023-05-04 Syngenta Crop Protection Ag Fungicidal compositions comprising fludioxonil
WO2023089049A2 (en) 2021-11-19 2023-05-25 Syngenta Crop Protection Ag Microbiocidal isonicotinic amide derivatives
WO2023094303A1 (en) 2021-11-25 2023-06-01 Syngenta Crop Protection Ag Microbiocidal heterobiaryl amide derivatives
WO2023094304A1 (en) 2021-11-25 2023-06-01 Syngenta Crop Protection Ag Microbiocidal heterobiaryl amide derivatives
WO2023099460A1 (en) 2021-12-02 2023-06-08 Syngenta Crop Protection Ag Fungicidal compositions
WO2023104714A1 (en) 2021-12-10 2023-06-15 Syngenta Crop Protection Ag Pesticidally active pyridazinone compounds
WO2023110710A1 (en) 2021-12-13 2023-06-22 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023110869A1 (en) 2021-12-15 2023-06-22 Syngenta Crop Protection Ag Microbiocidal bicycle heterocyclic derivatives
EP4197333A1 (en) 2021-12-15 2023-06-21 Syngenta Crop Protection AG Method for controlling diamide resistant pests & compounds therefor
WO2023111215A1 (en) 2021-12-17 2023-06-22 Syngenta Crop Protection Ag Microbiocidal pyridine-substituted benzothiazine derivatives
WO2023110871A1 (en) 2021-12-17 2023-06-22 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2023110928A1 (en) 2021-12-17 2023-06-22 Syngenta Crop Protection Ag Fungicidal compositions
WO2023118434A1 (en) 2021-12-22 2023-06-29 Globachem Nv Pesticidally active amide compounds
WO2023118011A1 (en) 2021-12-22 2023-06-29 Syngenta Crop Protection Ag Microbiocidal aza-heterobiaryl derivatives
WO2023117625A1 (en) 2021-12-22 2023-06-29 Syngenta Crop Protection Ag Fungicidal compositions
WO2023139166A1 (en) 2022-01-19 2023-07-27 Syngenta Crop Protection Ag Methods for controlling plant pathogens
WO2023148206A1 (en) 2022-02-02 2023-08-10 Syngenta Crop Protection Ag Microbiocidal n-amide derivatives
WO2023148369A1 (en) 2022-02-07 2023-08-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023148368A1 (en) 2022-02-07 2023-08-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023166067A1 (en) 2022-03-02 2023-09-07 Syngenta Crop Protection Ag Microbiocidal pyridazinone amide derivatives
WO2023187191A1 (en) 2022-04-01 2023-10-05 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023209238A1 (en) 2022-04-29 2023-11-02 Syngenta Crop Protection Ag Fungicidal compositions
WO2023217989A1 (en) 2022-05-12 2023-11-16 Syngenta Crop Protection Ag Alkoxy heteroaryl- carboxamide or thioamide compounds
WO2023247552A1 (en) 2022-06-21 2023-12-28 Syngenta Crop Protection Ag Microbiocidal bicyclic heterocyclic carboxamide derivatives
WO2023247360A1 (en) 2022-06-21 2023-12-28 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2024008567A1 (en) 2022-07-07 2024-01-11 Syngenta Crop Protection Ag Precision application devices and compositions
WO2024018016A1 (en) 2022-07-21 2024-01-25 Syngenta Crop Protection Ag Crystalline forms of 1,2,4-oxadiazole fungicides
WO2024017788A1 (en) 2022-07-22 2024-01-25 Syngenta Crop Protection Ag Solid form of a heterocyclic amide derivative
WO2024022910A1 (en) 2022-07-26 2024-02-01 Syngenta Crop Protection Ag 1-[1-[2-(pyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-3-[2,4-dichloro-5-phenyl]urea derivatives and similar compounds as pesticides
WO2024033374A1 (en) 2022-08-11 2024-02-15 Syngenta Crop Protection Ag Novel arylcarboxamide or arylthioamide compounds
WO2024038053A1 (en) 2022-08-16 2024-02-22 Syngenta Crop Protection Ag New use of pydiflumetofen
WO2024056732A1 (en) 2022-09-16 2024-03-21 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2024068655A1 (en) 2022-09-28 2024-04-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2024068838A1 (en) 2022-09-28 2024-04-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2024068656A1 (en) 2022-09-28 2024-04-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2024068950A1 (en) 2022-09-30 2024-04-04 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2024068947A1 (en) 2022-09-30 2024-04-04 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives

Also Published As

Publication number Publication date
AU2016239625B2 (en) 2019-10-03
EA201792145A1 (en) 2018-04-30
EP3274343A1 (en) 2018-01-31
JP2018513136A (en) 2018-05-24
AR104046A1 (en) 2017-06-21
MA40816A1 (en) 2017-10-31
IL254190B (en) 2019-08-29
PL3274343T3 (en) 2020-08-10
PT3274343T (en) 2020-05-07
CO2017009652A2 (en) 2018-02-20
BR112017020349A2 (en) 2018-07-17
CN107428722B (en) 2021-04-20
CN111892576A (en) 2020-11-06
KR20170131426A (en) 2017-11-29
CN107428722A (en) 2017-12-01
ES2935981T3 (en) 2023-03-13
CN111303116B (en) 2023-10-10
CA2978996A1 (en) 2016-10-06
EP3683213A1 (en) 2020-07-22
EA033690B1 (en) 2019-11-18
BR112017020349B1 (en) 2021-08-03
MX2017012195A (en) 2018-01-09
EP3274343B1 (en) 2020-03-04
IL254190A0 (en) 2017-10-31
CN111303116A (en) 2020-06-19
CL2017002426A1 (en) 2018-03-16
EP3848364A1 (en) 2021-07-14
AU2016239625A1 (en) 2017-09-21
ES2791193T3 (en) 2020-11-03
KR102565369B1 (en) 2023-08-08
US20180079740A1 (en) 2018-03-22
HUE049090T2 (en) 2020-09-28
TN2017000407A1 (en) 2019-01-16
CR20170418A (en) 2017-11-09
US10273221B2 (en) 2019-04-30
GEP20197032B (en) 2019-10-25
EP3683213B1 (en) 2022-10-12
JP6662901B2 (en) 2020-03-11
UA120960C2 (en) 2020-03-10

Similar Documents

Publication Publication Date Title
EP3274343B1 (en) Microbiocidal heterobicyclic derivatives
EP3114127B1 (en) Microbiocidal heterobicyclic derivatives
EP3681867B1 (en) Microbiocidal quinoline (thio)carboxamide derivatives
EP3102570B1 (en) Microbiocidal heterobicyclic derivatives
WO2019012011A1 (en) Microbiocidal oxadiazole derivatives
EP3681286B1 (en) Microbiocidal quinoline (thio)carboxamide derivatives
EP3681866A1 (en) Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053015A1 (en) Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053026A1 (en) Microbiocidal quinoline (thio)carboxamide derivatives
EP3334715B1 (en) Microbiocidal heterobicyclic derivatives
WO2019053027A1 (en) Microbiocidal quinoline (thio)carboxamide derivatives
EP3853207B1 (en) Microbiocidal quinoline carboxamide derivatives
WO2017178408A1 (en) Microbiocidal silicon containing aryl derivatives
EP3860993A1 (en) Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives
WO2020070132A1 (en) Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16711262

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 254190

Country of ref document: IL

WWE Wipo information: entry into national phase

Ref document number: 40816

Country of ref document: MA

ENP Entry into the national phase

Ref document number: 2978996

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: CR2017-000418

Country of ref document: CR

ENP Entry into the national phase

Ref document number: 20177026411

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2016239625

Country of ref document: AU

Date of ref document: 20160321

Kind code of ref document: A

REEP Request for entry into the european phase

Ref document number: 2016711262

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: NC2017/0009652

Country of ref document: CO

WWE Wipo information: entry into national phase

Ref document number: MX/A/2017/012195

Country of ref document: MX

ENP Entry into the national phase

Ref document number: 2017550509

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 15561788

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: A201710269

Country of ref document: UA

ENP Entry into the national phase

Ref document number: 14613

Country of ref document: GE

WWE Wipo information: entry into national phase

Ref document number: 201792145

Country of ref document: EA

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112017020349

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 112017020349

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20170922