WO2018210659A1 - Heteroaryl compounds as agrochemical fungicides - Google Patents

Heteroaryl compounds as agrochemical fungicides Download PDF

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WO2018210659A1
WO2018210659A1 PCT/EP2018/062031 EP2018062031W WO2018210659A1 WO 2018210659 A1 WO2018210659 A1 WO 2018210659A1 EP 2018062031 W EP2018062031 W EP 2018062031W WO 2018210659 A1 WO2018210659 A1 WO 2018210659A1
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phenyl
unsubstituted
substituted
group
alkyl
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PCT/EP2018/062031
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French (fr)
Inventor
Manojkumar POONOTH
Joachim Rheinheimer
Rakesh RATH
Claudia Rosenbaum
Christine WIEBE
Lutz Brahm
Georg Christoph RUDOLF
Smriti KHANNA
Egon Haden
Franz Roehl
Isabella SIEPE
Doris KREMZOW-GRAW
Helmut Schiffer
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Basf Se
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—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
    • A01N43/82—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 three ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to heteroaryl compounds of formula (I) or a compound in the form of a stereoisomer, an agriculturally acceptable salt, a tautomer, an isotopic form, a N-oxide, a S-oxide, or a prodrug thereof; and the use of a compound of formula (I) and a compound of formula (II) or in the form of a stereoisomer, an agriculturally acceptable salt, a tautomer, an isotopic form, a N-oxide, a S-oxide, or a prodrug thereof, as an agrochemical fungicide.
  • the in- vention further relates to agrochemical mixtures comprising at least one compound of formula (I); at least one further pesticidally active substance selected from the group consisting of herbicides, safeners, fungicides, insecticides, and plant growth regulators; and to agrochemical compositions comprising at least one such compound of the formula I and an auxiliary.
  • phytopathogenic harmful fungi which meth- ods comprising the steps of treatment of the phytopathogenic fungi, the plant or the plant propa- gation material selected from seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants to be protected against fungal attack, stored materials or harvest, or alternately the locus or soil or soil substituents or surfaces there- from, with at least one compound of formula (I).
  • Streptochlorin an indole alkaloid produced by many species of marine actinomycetes, was first isolated as a new antibiotic in 1988 from the lipophilic extracts of the mycelium of a Strepto- myces species.
  • Streptochlorin belongs to the class of naturally occurring 5-(3-indolyl) oxazoles, which also includes the natural product pimprinine.
  • Streptochlorin has been claimed to have a variety of biological activities, such as antibiotic, antiallergic, antiangiogenic, anticancer, anti- tumor, antiproliferative, antityrosinase, antinematodal and pesticidal activity.
  • Synthetic structural analogues of streptochlorin and pimprinine are known in the art to exhibit antifungal activity(Ming Zhi Zhang et al., Eur J. Med. Chem.92, 2015, 776-783).
  • US 2011207732 A1 discloses azaindole derivatives which are useful as medicaments. There is a continuous need for developing new fungicidal compounds which are effective in terms of activity spectrum, selectivity, sites of action, application rate, environmental safety and to retard or combat resistance development. In many cases, in particular at low application rates, the fungicidal activity of known fungicidal compounds is unsatisfactory
  • the novel heteroaryl compounds of formula (I) have improved antifungal activity.
  • the compounds are particularly effective as agrochemical fungicides and effective against a broad spectrum of phytopathogenic fungi.
  • the compounds of formula (I) also effectively exhibit phytopathogenic fungal activity against pathogens which are resistant to complex 2 or complex 3 respiratory chain inhibitors. Accordingly, the present invention relates to the use of an heteroaryl compound of formula (I), wherein,
  • X denotes CR 4 or N
  • Y denotes CR 5 or N
  • A is selected from the group consisting of an unsubstituted or substituted 6-membered aryl; unsubstituted or substituted 5- or a 6-membered heterocycloalkyl; unsubstituted or substituted 5 or a 6-membered heterocycloalkenyl; and a unsubstituted or substi- tuted 5- or a 6-membered heteroaryl; wherein heterocycloalkyl, heterocycloalkenyl and heteroaryl contain besides carbon atoms, 1, 2, 3 or 4 heteroatoms independently selected from O, N or S as ring members;
  • R 5 is selected from the group consisting of hydrogen; halogen; CN; unsubstituted or sub- stituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted al- kynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloal- kenyl; unsubstituted or substituted heterocycloalkyl and unsubstituted or substituted heterocycloalkenyl;
  • R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 and R 25 are independently of each other, selected from the group consisting of hydrogen; hal- ogen; CN; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; un- substituted or substituted alkynyl; unsubstituted or substituted cycloalkyl; unsubsti- tuted or substituted cycloalkenyl; unsubstituted or substituted aryl; unsubstituted or substituted -(alkylene)-aryl; unsubstituted or substituted heterocycloalkyl; unsubsti- tuted or substituted heterocycloalkenyl; unsubstituted or substituted heteroaryl
  • R 17 together with R 18 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
  • R 19 together with R 20 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
  • R 21 together with R 22 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
  • a 0, 1, 2 or 3;
  • b 0, 1, 2 or 3;
  • c 0, 1, 2 or 3;
  • d 0, 1, 2 or 3;
  • e 0, 1, 2 or 3;
  • f 0, 1, 2 or 3;
  • g 0, 1, 2 or 3;
  • h is 1, 2 or 3;
  • i 1, 2 or 3;
  • j 0, 1, 2 or 3;
  • k 0, 1, 2 or 3;
  • l 0, 1, 2 or 3;
  • n 0, 1, 2 or 3;
  • n 0, 1, 2 or 3;
  • o 1, 2 or 3;
  • the present invention relates to a composition, comprising at least one compound of formula (I) as defined herein above or in the form of a stereoisomer or an agricul- turally acceptable salt or a tautomer or an isotopic form of a N-oxide or a S-oxide or a prodrug thereof, and an auxiliary.
  • the present invention relates to an agrochemical mixture comprising at least one fertilizer; and at least one compound of formula (I) as defined herein above; or in the form of a stereoisomer or an agriculturally acceptable salt or a tautomer or an isotopic form or a N-oxide or a S-oxide or a prodrug thereof, and at least one pesticidally active substance selected from the group consisting of herbicides, safeners, fungicides, insecticides and plant growth regu- lators.
  • the present invention relates to a method for combating phytopathogenic harmful fungi, which process comprises treating the phytopathogenic fungi, the plant, or the plant propagation material selected from seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants to be protected against fungal attack, the stored materials or harvest, or alternately, the locus or soil or soil substituents or sur- faces therefrom, with an effective amount of at least one compound of formula (I) or an agricul- turally acceptable salt thereof or a tautomer or an isotopic form or a N-oxide or a S-oxide or a prodrug.
  • the plant propagation material selected from seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants to be protected against fungal attack, the stored materials or harvest, or alternately, the locus or soil or soil substituents or sur- faces therefrom, with
  • the term “consisting of” is considered to be a preferred embod- iment of the term “comprising of”. If hereinafter a group is defined to comprise at least a certain number of embodiments, this is meant to also encompass a group which preferably consists of these embodiments only. Furthermore, the terms “first”, “second”, “third” or “(a)”, “(b)”, “(c)”, “(d)” etc. and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be under- stood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein.
  • first”, “second”, “third” or “(a)”, “(b)”, “(c)”, “(d)”, “i”, “ii” etc. relate to steps of a method or use or assay there is no time or time interval coherence between the steps, i.e. the steps may be carried out simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between such steps, unless oth- erwise indicated in the application as set forth herein above or below. It is to be understood that this invention is not limited to the particular methodology, protocols, reagents etc. described herein as these may vary.
  • substitution′′, ⁇ substituted′′ or ⁇ substituted with means that one or more hydrogens of the specified moiety are replaced with a suitable substituent and includes the implicit proviso that such substitutions is in accordance with permitted valence of the substi- tuted atom and the substituent and results in a stable compound.
  • alkyl′′ as used herein, alone or as part of a substituent group refers to an acylic saturated aliphatic groups, including straight-chain or branched alkyl residues.
  • alkyl residue can be unsubstituted or substituted with one or more substituents, as in the case of C 1- C 6- alkyl, 1 to 6 carbon atoms.
  • substituents deonote an alkyl residue or comprise an alkyl residue which is mono or polysubsti- tuted
  • alkyl which may be unsubstituted or mono- or polysubstituted include, but not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexytl, isopropyl, isobutyl, tertiary butyl, isopentyl, 2-methylbutyl, 3-methylbutyl and the like.
  • Polysubstituted alkyl residues are understood to be those alkyl residues which are polysubstituted, preferably di- or trisubsti- tuted, either on different or on the same carbon atoms, for example trisubstituted on the same C atom as in the case of -CF3 or at different locations as the case of–(CHCl)-(CH2)F. Polysubstitu- tion may proceed with identical or different substituents.
  • alkenyl′′ refers to acyclic unsaturated hydrocarbon residues, including straight-chain or branched alkenyl residues, and comprise at least one double bond, preferably 1, 2, or 3 double bonds, with as in the case of C2 C6 alkenyl, 2 to 6 C atoms.
  • the alkenyl residue can be unsubstituted or substi tuted with one or more substituents, as in the case of C2-C6-alkenyl, 2 to 6 carbon atoms.
  • substituents denote an alkenyl residue or comprise an alkenyl residue which is mono or polysubstituted
  • substituted alkyl examples include but not limited to methyl, ethyl, hy- droxymethyl, 2-chlorobutyl, fluoromethyl, 1,1-difluoromethyl, trifluoromethyl, trichloromethyl, 1,1,1,2,2-pentafluoroethyl, 1,1,2,2– tetrafluoroethyl or aminomethyl.
  • alkynyl′′ refers to acyclic unsaturated hydrocarbon residues, including straight-chain or branched alkenyl residues, and comprise at least one triple bond, preferably 1 or 2 triple bonds, with as in the case of C 2 -C 6 alkynyl, 2 to 6 C atoms.
  • the alkynyl residue can be unsubstituted or substituted with one or more substituents, as in the case of C2-C6-alkynyl, 2 to 6 Carbon atoms.
  • alkynyl which may be unsubstituted or mono- or polysubsti- tuted include, but not limited to, ethynyl, 1-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, hexynyl and the like.
  • Polysubstituted alkynyl residues are un- derstood to be those alkynyl residues which are polysubstituted, preferably disubstituted, either on different or on the same carbon atoms.
  • Representative examples of alkynyl residues include, but not limited to, -C ⁇ C-Si(CH3)3, -C ⁇ C-Si(CH2)2-CH3 and -C ⁇ C-Si(CH2)2-C6H5.
  • heteroalkyl′′ denotes an alkyl residue described hereinabove, in which one or more C atoms have been replaced by a heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur.
  • Heteroalkyl resi- dues may preferably comprise 1, 2, 3, 4, 5 or 6 carbon atoms and 1, 2 or 3 heteroatom(s) inde- pendently of each other selected from the group consisting of oxygen, nitrogen and sulfur.
  • Par- ticularly preferred heteroalkyl residues may be 2 to 6-membered.
  • heteroalkyl residues which may in each case by un- substituted or mono- or polysubstituted, are -O-CH3, -O-CH2-CH3, -CH2-O-CH3, -CH2-O-C2H5, - CH2-O-CH(CH3)2, -CH2-O-CH3, -CH2-S-CH3, -CH2-NH-CH3, -CH2-NH-C2H5, -CH2-NH-CH(CH3)2, - CH 2 -NH-CH 3 , -CH 2 -NH-(CH 3 ) 3 , -CH 2 -CH 2 -O-CH 3 , -CH 2 -CH 2 -O-C 2 H 5 , -CH 2 -CH 2 -O-CH(CH 3 ) 2 , - CH2-CH2-O-(CH3)3, -CH2-CH2-S-CH3, -CH2-CH2-S-C2H5, -CH2-CH2-S-CH(CH3)2, -CH2-CH2-CH3,
  • heteroalkenyl′′ refers to an alkenyl residue described hereinabove, in which one or more C atoms have been replaced by a heteroatom independently selected from the group consisting of oxygen, nitrogen and sulfur.
  • Heteroalkenyl residues may preferably comprise 1, 2, 3, 4, 5 or 6 carbon atoms and 1, 2 or 3 heteroatom(s) independently of each other selected from the group consisting of oxygen, nitrogen and sulfur as chain links and may preferably be 2- to 6-membered.
  • heteroalkynyl refers to an alkenyl residue described hereinabove, in which one or more C atoms have been replaced by a heteroatom independently of each other selected from the group consisting of oxygen, nitro- gen and sulfur.
  • Heteroalkenyl residues may preferably comprise 1, 2, 3, 4, 5 or 6 carbon atoms and 1, 2 or 3 heteroatom(s) independently selected from the group consisting of oxygen, nitrogen and sulfur as chain links and may preferably be 2- to 6-membered.
  • suitable heteroalkynyl residues may include, but not limited to, -CH 2 -O-C ⁇ CH, -CH 2 -S-C ⁇ CH, - CH2-CH2-O-C ⁇ CH and–CH2-CH2-S-C ⁇ CH.
  • cycloalkyl refers to a saturated cyclic hydrocarbon residue including preferably 3, 4, 5, 6, 7, 8, 9 or 10 C atoms, as ring members; and more preferably refers to a cycloalkyl with 3, 4, 5, 6 or 7 carbon atoms.
  • the cycloalkyl group may be unsubstituted or monosubstituted or identically or differently polysubsti- tuted.
  • Representative examples of cycloalkyl include, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.
  • cycloalkyl refers to a cyclic unsaturated hydrocarbon residue including preferably 3, 4, 5, 6, 7, 8, 9 or 10 C atoms, as ring members; and more preferably refers to a cycloalkyl with 3, 4, 5, 6 or 7 carbon atoms.
  • the cycloalkenyl group may be unsubstituted or monosubstituted or identically or differently pol- ysubstituted.
  • cycloalkenyl include, but not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl cyclohexadienyl, cycloheptenyl and cycloheptadienyl.
  • heterocycloalkyl′′ refers to a cyclic saturated hydrocarbon residue with preferably 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, preferably with 3, 4, 5, 6 or 7 carbon atoms, wherein, one or more C atoms are replaced heteroatoms independently selected from oxygen, nitrogen and sulfur.
  • Heterocycloalkyl residues may preferably comprise 1, 2, or 3 heteroatom(s) mutually independently selected from the group consisting of oxygen, sulfur and nitrogen as ring members.
  • a heterocycloalkyl residue may be unsubstituted or monosubstituted or identically or differently polysubstituted.
  • Heterocycloalkyl res- idues may preferably be 3 to 7 membered and more preferably 5 to 7-membered.
  • heterocycloalkyls include, but not limited to, tetrahydrofuranyl, tetrahydrothiophenyl, tetrahydropyranyl, oxetanyl, piperidinyl, piperazinyl, morpholinyl, thiomor- pholinyl, 1,2,4-oxadiazonyl, 1,2,4-thiodiazonyl, 1,3,4-trimethyl piperazinyl, 2-piperidinyl, 3-piperi- dinyl, 4-piperidinyl, 1,3-dioxan-5-yl, tetrahydropyrimidinyl, tetrahydropyrazinyl and tetrahydro- pyridazinyl.
  • heterocycloalkenyl ′′ refers to a cyclic unsaturated hydrocarbon residue with preferably 4, 5, 6, 7, 8, 9 or 10 carbon atoms, preferably with 4, 5, 6 or 7 carbon atoms, which comprises at least one double bond, and wherein, one or more C atoms are replaced by heteroatoms independently selected from oxygen, nitrogen and sulfur.
  • Heterocycloalkenyl residues may preferably comprise 1, 2, or 3 heteroatom(s) mutually independently selected from the group consisting of oxygen, sulfur and nitrogen as ring members.
  • a heterocycloalkenyl residue may be unsubstituted or monosubstituted or identically or differently polysubstituted.
  • Heterocycloalkenyl residues may preferably be 4 to 9 membered and more preferably 5 to 7-membered.
  • heterocycloalkenyls include, but not limited to, (2,3)-dihydro- furanyl, (2,3)-dihydrothienyl, (2,3)-dihydropyrrolyl, (2,5)-dihydropyrrolyl, (2,5)-dihydropyrrolyl, (2,3) dihydroisoxazolyl, (1,4) dihydropyridin 1 yl, dihydropyranyl, 2,3 dihydropyrazol 1 yl, 2,3 di hydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4- dihydropyrazol-1-yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyra
  • cycloalkyl, heterocycloalkyl, cycloalkenyl or heterocycloalkenyl residues may be fused with an unsubstituted or at least monosubstituted mono- or bicyclic ring system.
  • a mono- or bicyclic ring system should be understood to mean mono- or bicyclic hydrocarbon residues which may be saturated, unsaturated or aromatic and optionally comprise one or more heteroatoms as ring members.
  • the above-stated mono- or bicyclic ring systems are 4-, 5- or 6-membered and may in each case preferably optionally comprise 0, 1, 2, 3, 4, or 5 heteroatoms, specifically, optionally 0, 1 or 2 heteroatoms as ring members, inde- pendently selected from the group consisting of oxygen, nitrogen and sulfur.
  • the different rings may, in each case may indepedendently exhibit a different degree of saturation, i.e. be saturated, unsaturated or aromatic.
  • substituents comprise a monocyclic or bicyclic ring system, which is mono- or polysubstituted
  • aryl′′ refers to a monocyclic, bicyclic or tricyclic hydrocarbon ring system having 6, 10 or up to 14 ring carbon atoms, wherein at least one carbocyclic ring is having a ⁇ -electron system.
  • An aryl residue may be unsubstituted, monosubstituted or identically or differently polysubstituted. Examples of phenyl residues include, phenyl, 1-naphthyl, 2-naphthyl or anthracenyl.
  • heteroaryl′′ refers to an aromatic monocyclic, bicyclic or a tricyclic hydrocarbon containing 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms, particularly, preferably with 5, 6, 9 or 10 atoms and more particularly, with 5 or 6 carbon atoms, in which one to four carbon atoms are replaced by identical or different hetero atoms selected from the group consisting of oxygen, sulfur and nitrogen.
  • Heteroaryl resi- dues may preferably comprise 1, 2, 3, 4 or 5, particularly preferably 1, 2, or 3, heteroatoms inde- pendently selected from the group consisting of oxygen, sulfur and nitrogen.
  • a heteroaryl residue may be unsubstituted or monosubstituted or identically or differently polysubstituted.
  • heteroaryl residues include, but not limited to, furyl, pyridyl, oxazolyl, thiazolyl, pyrazolyl, pyrimidinyl, pyrrolyl, isooxazolyl, triazolyl, tetrazolyl, pyridazi- nyl, isothiazolyl, benzothiazolyl, benzooxazolyl, benzimidazolyl, quinolinyl or isoquinolinyl.
  • aryl or heteroaryl residues may be fused with a mono- or bicyclic ring system defined as above.
  • Representative examples of aryl rings fused with a mono or bicyclic ring system include, but not limited to, 2,3-dihydrobenzo[b]thiophenyl, 2,3-dihydro-1H-indenyl, indolinyl, 2,3-dihydro- benzofuranyl, 2,3-dihydrobenzo[d]oxazolyl, benzo[d][1,3]dioxolanyl, isoindolinyl, 1,2,3,4- tetrahy- dronaphthyl, 1,2,3,4 tetrahydroquinolinyl, 1,2,3,4-tetrahydroisoquinolinyl, chromanyl, thiochroma- nyl, 3,4-dihydro-2H-benzo[1,4]oxazinyl and 3,4-d
  • Aryl radicals may be substituted in any desired position.
  • the substitutent may be located in the 2-position, the 3-position, the 4-position or the 5- position. If the phenyl carries two substituents, they can be located in 2, 3-position, 2, 4- position, 2, 5-position, 2, 6-position, 3, 4-position or 3, 5-position.
  • monosub- stituted and polysubstituted phenyl groups include, but not limited to, 2-fluorophenyl, 3-fluoro- phenyl, 4-fluorophenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2-aminophenyl, 3- aminophenyl, 4-aminophenyl, 2-dimethylaminophenyl, 2-dimethylaminophenyl, 3-dimethyla- minophenyl, 4-dimethylaminophenyl, 2-methylsulfinyl phenyl, 3-methylsulfinyl phenyl, 4-methyl- sulfinyl phenyl, 2-methylsulfonyl phenyl, 3-methylsulfonyl phenyl, 4-methylsulfonyl phenyl, 2- methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-carboxy phenyl, 3-
  • heteroatom as used herein, includes nitrogen (N), oxygen (O) and sulfur (S). Any heteroatom with unsatisfied valency is assumed to have a hydrogen atom or a C 1 -C 6 -alkyl group to satisfy the valency.
  • stereoisomer is a general term used for all isomers of individual compounds that differ only in the orientation of their atoms in space.
  • stereoisomer includes mirror image isomers (enantiomers), mixtures of mirror image isomers (racemates, racemic mixtures), geometric (cis/trans or E/Z) isomers, and isomers of compounds with more than one chiral center that are not mirror images of one another (diastereoisomers).
  • tautomer refers to the coexistence of two (or more) compounds that differ from each other only in the position of one (or more) mobile atoms and in electron distribution, for example, keto-enol tautomers.
  • agriculturally acceptable salts includes salts of the active com- pounds which are prepared with acids or bases, depending on the particular substituents found on the compounds described herein.
  • isotopic forms or“isotopically labeled forms” is a general term used for isotopic forms of compounds of formula, wherein one or more atoms of compounds of formula (I); I(A); I(B); I(C); I(D); I(E); I(F); I(G); I(H); I(I); I(J); I(K); I(L); I(M); I(N); I(O); I(P); I(Q); I(R); I(S); I(T); I(U), are replaced by their respective isotopes. All isotopes of any particular atom or element as specified are contemplated within the scope of the compounds of the invention.
  • isotopes examples include, but are not limited to, isotopes of hydrogen such as 2 H (deuterium or D) and 3 H, carbon such as 11 C, 13 C and 14 C, nitrogen such as 13 N and 15 N, oxygen such as 15 O, 17 O and 18 O, chlorine such as 36 Cl, fluorine such as 18 F and sulphur such as 35 S.
  • isotopes of hydrogen such as 2 H (deuterium or D) and 3 H
  • carbon such as 11 C, 13 C and 14 C
  • nitrogen such as 13 N and 15 N
  • oxygen such as 15 O, 17 O and 18 O
  • chlorine such as 36 Cl
  • fluorine such as 18 F and sulphur such as 35 S.
  • isotopic forms of the compounds of formula (I) may include, without limitation, deuterated compounds of formula I(A); I(B); I(C); I(D); I(E); I(F); I(G); I(H); I(I); I(J); I(K); I(L); I(M); I(N); I(O); I(P); I(Q); I(R); I(S); I(T); I(U).
  • deuterated as used herein, by itself or used to modify a compound or group, refers to replacement of one or more hydrogen atom(s), which is attached to carbon(s), with a deuterium atom.
  • the compounds of formula (I) or I(A) or I(B) or I(C) or I(D) or I(E) or I(F) or I(G) or I(H) or I(I) or I(J) or I(K) or I(L) or I(M) or I(N) or I(O) or I(P) or I(Q) or I(R) or I(S) or I(T) or I(U) may include in the definitions of one or more of the various variables, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 ,
  • N-oxide refers to the oxide of the nitrogen atom of a nitrogen-containing heteroaryl or heterocycle. N-oxide can be formed in the presence of an oxidizing agent for example peroxide such as m-chloro-perbenzoic acid or hydrogen peroxide. N-oxide refers to an amine oxide, also known as amine-N-oxide, and is a chemical compound that contains N ⁇ O bond.
  • S-oxide refers to the oxide of the sulfur atom (S-oxide) or dioxide of the sulfur atom (S,S-dioxide) of a sulfur-containing het- eroaryl or heterocycle.
  • S-oxide and S,S-dioxides can be in the presence of an oxidizing agent for example peroxide such as m-chloro-perbenzoic acid or oxone.
  • prodrug refers to compounds of formula (I), that are compound precursors, which following appli- cation, release the active ingredient or the parent compound via a chemical or metabolic process, for example, a prodrug on being brought to the physiological pH or through an enzyme action is converted to the desired active ingredient having the fungicidal effect.
  • bio-cleavable amino protecting group is intended to refer to a group that can be selectively attached to the nitrogen atom by chemical modification of an amino group so as to selectively inhibit participation of the amino group in chemical reactions.
  • these amino protecting groups can be cleaved either chemically or enzymatically.
  • Exemplary bio-cleavable amino-protecting groups include car- bamates (urethanes) selected from methyl, ethyl and tertiary butyl (i.e. BOC or tert-butoxy car- bonyl) and amides selected from acetyl and methoxyacetyl.
  • the present invention relates to the use of an heteroaryl compound of formula (I),
  • X denotes CR 4 or N
  • Y denotes CR 5 or N
  • A is selected from the group consisting of an unsubstituted or substituted 6-membered aryl; unsubstituted or substituted 5- or a 6-membered heterocycloalkyl; unsubstituted or substituted 5 or a 6-membered heterocycloalkenyl; and a unsubstituted or substi- tuted 5- or a 6-membered heteroaryl; wherein heterocycloalkyl, heterocycloalkenyl and heteroaryl contain besides carbon atoms, 1, 2, 3 or 4 heteroatoms independently selected from O, N or S as ring members;
  • R 4 is selected from the group consisting of hydrogen and halogen
  • R 5 is selected from the group consisting of hydrogen; halogen; CN; unsubstituted or sub- stituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted al- kynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloal- kenyl; unsubstituted or substituted heterocycloalkyl and unsubstituted or substituted heterocycloalkenyl;
  • R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 and R 25 are independently of each other, selected from the group consisting of hydrogen; hal- ogen; CN; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; un- substituted or substituted alkynyl; unsubstituted or substituted cycloalkyl; unsubsti- tuted or substituted cycloalkenyl; unsubstituted or substituted aryl; unsubstituted or substituted -(alkylene)-aryl; unsubstituted or substituted heterocycloalkyl; unsubsti- tuted or substituted heterocycloalkenyl; unsubstituted or substituted heteroaryl
  • R 17 together with R 18 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
  • R 19 together with R 20 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substituted; or
  • R 21 together with R 22 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substituted;
  • a 0, 1, 2 or 3;
  • b 0, 1, 2 or 3;
  • c 0, 1, 2 or 3;
  • d 0, 1, 2 or 3;
  • e 0, 1, 2 or 3;
  • f 0, 1, 2 or 3;
  • g 0, 1, 2 or 3;
  • h is 1, 2 or 3;
  • i 1, 2 or 3;
  • j 0, 1, 2 or 3;
  • k 0, 1, 2 or 3;
  • n 0, 1, 2 or 3;
  • o 1, 2 or 3;
  • the present invention encompasses the use of a an heteroaryl compound of formula (I), wherein,
  • X, Y, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 and R 25 , a, b, c, d, e, f, g, h, I, j, k, l, m, n and o are as defined in the first embodiment hereinabove;
  • A is selected from the group consisting of:
  • R 115 and R 116 are independently of each other selected from the group consisting of H; halogen; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubsti- tuted or substituted alkynyl; unsubstituted or unsubstituted or substituted cycloalkyl; unsub- stituted or substituted cycloalkenyl; unsubstituted or substituted heterocycloalkyl; and unsub- stituted or substituted heterocycloalkenyl; and whereby,
  • the alkyl are straight-chain or branched, and comprise 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms as chain links;
  • the alkenyl are straight chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
  • alkynyl are straight-chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
  • heteroalkyl, heteroalkenyl and heteroalkynyl comprise 1, 2, 3, 4, 5 or 6 carbon atoms and 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from O, N(H) or S as chain links;
  • the cycloalkyl and cycloalkenyl comprises 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms as ring mem- bers;
  • heterocycloalkyl and heterocycloalkenyl are 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from the group consisting of O, N(H) and S as ring members;
  • the aryl are mono-, bicyclic or tricyclic and comprise 6, 10 or 14 carbon atoms;
  • heteroaryl are mono- or bicyclic and 5- or 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently selected from the group consisting of O, N(H) or S as ring members;
  • R 115 and R 116 are independently of each other selected from the group consisting of H;
  • halogen unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substituted heterocycloalkyl; and unsubstituted or substituted heterocycloalkenyl;
  • A is selected from the group consisting of:
  • X is CR 4 ;
  • Y is CR 5 ;
  • A is selected from the group consisting of:
  • the present invention encompasses the use of compounds of formula (I
  • X is CR 4 ;
  • Y is CR 5 ;
  • A is selected from the group consisting of:
  • X is CR 4 ;
  • Y is CR 5 ;
  • A is selected from the group consisting of:
  • R 1 is hydrogen;
  • R 2 is hydrogen;
  • the present invention encompasses the use of compounds of formula (I), wherein, R 1 is hydrogen. In a yet further embodiment, the present invention encompasses the use of compounds of formula (I), wherein, R 1 is hydrogen. In a yet further embodiment, the present invention encompasses the use of compounds of formula (I), wherein, R 1 is hydrogen. In a yet further embodiment, the present invention encompasses the use of compounds of formula (I), wherein, R 1 is hydrogen. In a yet further embodiment, the present invention encompasses the use of compounds of formula (I), wherein, R 1 is hydrogen. In a yet further embodiment, the present invention encompasses the use of compounds of formula (I), wherein, R 1 is hydrogen. In a yet further embodiment, the present invention encompasses the use of compounds of formula (I), wherein, R 1 is hydrogen. In a yet further embodiment, the present invention encompasses the use of compounds of formula (I), wherein, R 1 is hydrogen. In a yet further embodiment, the present invention encompasses the use of compounds of formula (I
  • the present invention encompasses the use of compounds of formula (I), wherein
  • R 14 is selected from the group consisting of hydrogen; halogen; CN; unsubstituted or sub- stituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; un- substituted or substituted aryl; unsubstituted or substituted -(alkylene)-aryl; unsubsti- tuted or substituted heterocycloalkyl; unsubstituted or substituted heterocycloalkenyl; unsubstituted or substituted heteroaryl; wherein, alkyl, alkenyl and alkynyl is unsubsti- tuted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of wherein alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently
  • the present invention encompasses the use of compounds of formula (I), wherein
  • the present invention encompasses the use of compounds of for- mula (I), wherein
  • the present invention encompasses the compounds of formula (I), wherein, R 2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -CF 3 ; -CCl 3 ; -CHF 2 ;
  • the present invention encompasses the use of compounds of formula (I), wherein,
  • the present invention encompasses the use of compounds of formula (I), wherein,
  • the present invention encompasses the use of compounds of formula (I), wherein, R 4 is selected from the group consisting of hydrogen and halogen.
  • the present invention encompasses the use of compounds of formula (I), wherein, R 4 is selected from the group consisting of hydrogen, F; Cl; Br and I.
  • R 5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; methyl, ethyl, pro- pyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, tetrahydro- furanyl, tetrahydrothiophenyl, tetrahydropyranyl, oxetanyl, piperidinyl, piperazinyl, morpholinyl
  • the present invention encompasses the use of compounds of formula (I), wherein,
  • R 5 is selected from the group consisting of hydrogen, F; Cl; Br; I; CN; -CF 3 ; -CHF 2 ; - CH(F)-CF3; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, iso- pentyl and tert butyl.
  • the present invention encompasses the use of compounds of formula (I), wherein, R 3 is selected from the group consisting of hydrogen, methyl, ethenyl, isopropenyl, ethynyl and cyclopropyl; and the remaining of R 4 and R 5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; -CF3; -CHF2; -CH(F)-CF3; methyl, ethyl, pro- pyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl and tert butyl; or R is selected from the group consisting of hydrogen, F; Cl; Br and I; and the remaining of R 3 and R 5 are independently of each other selected from the group consisting of methyl, ethenyl, isopropenyl, ethynyl, and cyclopropyl;
  • R 3 and R 4 are independently of each other is selected from the group consisting of hydrogen; methyl, ethenyl, iso- propenyl, ethynyl and cyclopropyl.
  • the present invention encompasses the use of compounds of formula (I), wherein, R 3 is selected from the group consisting of hydrogen, methyl, ethenyl, isopropenyl, ethynyl and cyclopropyl; and the remaining of R 4 and R 5 are independently of each other selected from the group consisting of hydrogen; or R 4 is hydrogen; and the remaining of R 3 and R 5 are independently of each other selected from the group consisting of methyl, ethenyl, isopropenyl, ethynyl, and cyclopropyl; or R 5 is hydrogen; and the remaining of R 3 and R 4 are independently of each other is se- lected from the group consisting of hydrogen; methyl, ethenyl, isopropenyl, ethynyl and cyclopropyl.
  • the present invention encompasses the use of compounds of formula (I), wherein,
  • R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 and R 25 are independently of each other, selected from the group consisting of hydrogen; halogen; CN; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or substituted cycloalkyl; unsubsti- tuted or substituted cycloalkenyl; unsubstituted or substituted aryl; unsubstituted or substituted -(alkylene)-aryl; unsubstituted or substituted heterocycloalkyl; unsubsti- tuted or substituted heterocycloalkenyl; unsubstituted or substituted heteroaryl
  • the present invention encompasses the use of compounds of formula (I), wherein,
  • R 6 R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 and R 25 is selected from the group consisting of hydrogen; Cl, F, Br, I, NH2, -NH-CH3, -N(CH3)2, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, tert butyl, ethenyl, pro- penyl, butenyl, isopropenyl, isopentenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobu- tyl, cyclopentyl, cyclohexyl, furyl, oxazolyl
  • the present invention encompasses the use of compounds of for- mula (I), wherein,
  • R 6 R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 and R 25 is selected from the group consisting of hydrogen; Cl, F, Br, I, NH 2 , -NH-CH 3 , -N(CH 3 ) 2 , methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, tert butyl, ethynyl, cyclopropyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; wherein, the alkyl, alkenyl and alkynyl is unsubstituted or substituted with
  • the present invention encompasses the use of compounds of formula (I), wherein
  • X denotes CR 4 and Y denotes CR 5 ;
  • X denotes N and Y denotes CR 5 ;
  • X denotes CR 4 and Y denotes N;
  • X denotes N and Y denotes N;
  • the present invention encompasses the use of the compounds of formula (I), wherein,
  • R 6 R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 and R 25 is selected from the group consisting of hydrogen; Cl, F, Br, I, NH 2 , -NH-CH 3 , -N(CH 3 ) 2 , methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, tert butyl, ethynyl, cyclopropyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; wherein, the alkyl is unsubstituted or substituted with -Si-(CH3)3; the
  • R 115 and R 116 are independently of each other selected from the group consisting of H; halogen; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubsti- tuted or substituted alkynyl; unsubstituted or unsubstituted or substituted cycloalkyl; unsub- stituted or substituted cycloalkenyl; unsubstituted or substituted heterocycloalkyl; and unsub- stituted or substituted heterocycloalkenyl; and whereby,
  • the alkyl are straight-chain or branched, and comprise 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms as chain links;
  • alkenyl are straight-chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
  • alkynyl are straight-chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
  • heteroalkyl, heteroalkenyl and heteroalkynyl comprise 1, 2, 3, 4, 5 or 6 carbon atoms and 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from O, N(H) or S as chain links;
  • the cycloalkyl and cycloalkenyl comprises 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms as ring mem- bers;
  • heterocycloalkyl and heterocycloalkenyl are 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from the group consisting of O, N(H) and S as ring members;
  • the aryl are mono-, bicyclic or tricyclic and comprise 6, 10 or 14 carbon atoms;
  • heteroaryl are mono- or bicyclic and 5- or 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently selected from the group consisting of O, N(H) or S as ring members;
  • the present invention encompasses the use of the compounds of formula (I), wherein,
  • the present invention encompasses the use of compounds of formula (I), is a compound of formula I(A),
  • X and Y are as defined as in the third embodiment hereinabove;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 71 , R 72 , R 73 and R 74 , a, b, c, d, e, f, g, h, I, j, k, l, m, n and o are as defined in the second embodiment hereinabove;
  • R 3 is selected from the group consisting of hydrogen, Cl; F; Br; I; -CN; -O-CH 3 ; -O-CH 2 - CH 3 ; -C(CH 3 ) 2 -OH; -CH(CH 3 )-OH; -CF 3 ; -CH(CF 3 )-OH; -CHF 2 ; -CH(F)-CF 3 ; -
  • the present invention encompasses the use of compounds of formula I(A), wherein, X is CR 4 ; Y is CR 5 ; R 1 is hydrogen; R 2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -CF 3 ; -CCl 3 ; -CHF 2 ;
  • R 3 is selected from the group consisting of hydrogen, methyl, ethenyl, isopropenyl, ethynyl and cyclopropyl; and the remaining of R 4 and R 5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; -CF3; -CHF2; -CH(F)-CF3; methyl, e
  • the present invention encompasses the use of compounds of formula I(A), selected from:
  • the present invention provides a use of an heteroaryl compound of formula (I),
  • X denotes N
  • Y denotes CR 5 or N
  • a together with the two carbon atoms of pyrrole ring, is selected from the group consist- ing of an unsubstituted or substituted 6-membered aryl;
  • R 5 is selected from the group consisting of hydrogen; halogen; CN; unsubstituted or sub- stituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted al- kynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloal- kenyl; unsubstituted or substituted heterocycloalkyl and unsubstituted or substituted heterocycloalkenyl;
  • R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 and R 25 , R 25’ , R 25’’ , R 25’’’ , R 25’’’’’’’’ are independently of each other, selected from the group con- sisting of hydrogen; halogen; hydroxy, CN; unsubstituted or substituted alkyl; unsub- stituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or sub- stituted aryl; unsubstituted or substituted -(alkylene)-aryl; unsubstitute
  • R 17 together with R 18 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substituted;
  • R 19 together with R 20 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl;
  • heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
  • R 21 together with R 22 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl;
  • heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
  • the present invention provides the use of a compound of formula (I), wherein,
  • R 115 and R 116 are independently of each other selected from the group consisting of H; hal- ogen; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsub- stituted or substituted alkynyl; unsubstituted or unsubstituted or substituted cycloal- kyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substituted heterocy- cloalkyl; and unsubstituted or substituted heterocycloalkenyl;
  • the alkyl are straight-chain or branched, and comprise 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms as chain links;
  • alkenyl are straight-chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
  • alkynyl are straight-chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
  • heteroalkyl, heteroalkenyl and heteroalkynyl comprise 1, 2, 3, 4, 5 or 6 carbon atoms and 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from O, N(H) or S as chain links;
  • the cycloalkyl and cycloalkenyl comprises 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms as ring members;
  • heterocycloalkyl and heterocycloalkenyl are 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from the group consisting of O, N(H) and S as ring members;
  • the aryl are mono-, bicyclic or tricyclic and comprise 6, 10 or 14 carbon atoms;
  • heteroaryl are mono- or bicyclic and 5- or 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently selected from the group consisting of O, N(H) or S as ring members;
  • X denotes N and Y denotes CR 5 ; or X denotes N and Y denotes N;
  • X denotes N and Y denotes CR 5 ;
  • X denotes N and Y denotes N;
  • the present invention provides the use of a compound of formula I(A), , wherein the compound is: 3-[5-(trifluoromethyl)isothiazol-4-yl]-1H-indole-5-carbonitrile; 3-[3- (trifluoromethyl)isothiazol-4-yl]-1H-indole-5-carbonitrile; 3-(3,5-dimethylisothiazol-4-yl)-1H-in- dole-5-carbonitrile; and 3-(5-methylthiadiazol-4-yl)-1H-indole-5-carbonitrile.
  • the present invention provides the use of a compound of formua (I), wherein,
  • R 1 is hydrogen;
  • R 2 is hydrogen;
  • A is:
  • R 1 is hydrogen;
  • R 2 is hydrogen;
  • R 3 is -CF 3 ;
  • R 71 , R 72 , R 73 and R 74 are independently of each other, selected from the group consisting of hy- drogen; Cl; F; Br; I; CN; methyl, ethynyl and propynyl.
  • the present invention provides the use of compound of formula (I), wherein,
  • A is:
  • R 1 is hydrogen;
  • R 2 is hydrogen;
  • R 3 is -CHF2 or CH2F;
  • R 71 , R 72 , R 73 and R 74 are independently of each other, selected from the group consisting of hy- drogen; Cl; F; Br; I; CN; methyl, ethynyl and propynyl.
  • the present invention provides a heteroaryl compound of formula (I), formula (I)
  • X denotes N
  • Y denotes CR 5 or N
  • R 5 is selected from the group consisting of hydrogen; halogen; CN; unsubstituted or sub- stituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted al- kynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloal- kenyl; unsubstituted or substituted heterocycloalkyl and unsubstituted or substituted heterocycloalkenyl;
  • R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 25 , R 25’ , R 25’’ , R 25’’ and R 25’’’’ are independently of each other, selected from the group consisting of hy- drogen; halogen; hydroxy, CN; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substituted aryl; unsubstituted or substituted -(alkylene)-aryl; unsubstituted or substituted heterocyclo- alkyl; unsubsti
  • R 17 together with R 18 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substituted;
  • R 19 together with R 20 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl;
  • heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
  • R 21 together with R 22 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substituted;
  • R 115 and R 116 are independently of each other selected from the group consisting of H; halo- gen; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubsti- tuted or substituted alkynyl; unsubstituted or unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substituted heterocycloal- kyl; and unsubstituted or substituted heterocycloalkenyl;
  • the alkyl are straight-chain or branched, and comprise 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms as chain links;
  • alkenyl are straight-chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
  • alkynyl are straight-chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
  • heteroalkyl, heteroalkenyl and heteroalkynyl comprise 1, 2, 3, 4, 5 or 6 carbon atoms and 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from O, N(H) or S as chain links;
  • heterocycloalkyl and heterocycloalkenyl are 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from the group consisting of O, N(H) and S as ring members;
  • the aryl are mono-, bicyclic or tricyclic and comprise 6, 10 or 14 carbon atoms;
  • heteroaryl are mono- or bicyclic and 5- or 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently selected from the group consisting of O, N(H) or S as ring members;
  • X denotes N and Y denotes N;
  • A is selected from the group consisting of:
  • R 1 is hydrogen; R 2 is hydrogen; R 3 is selected from the group consisting of Cl; F; Br; I; -CN;
  • the present invention provides the compound of formula I(A), wherein the compound is: 3-[5-(trifluoromethyl)isothiazol-4-yl]-1H-indole-5-carbonitrile; 3-[3-(trifluoro- methyl)isothiazol-4-yl]-1H-indole-5-carbonitrile; 3-(3,5-dimethylisothiazol-4-yl)-1H-indole-5-car- bonitrile; and 3-(5-methylthiadiazol-4-yl)-1H-indole-5-carbonitrile.
  • the present invention provides the compound of formula (I), wherein, X is N; Y is CH or N
  • A is:
  • R 1 is hydrogen;
  • R 2 is hydrogen;
  • R 3 is -CF 3 ;
  • R 71 , R 72 , R 73 and R 74 are independently of each other, selected from the group consisting of hy- drogen; Cl; F; Br; I; CN; methyl, ethynyl, propynyl.
  • the present invention provides the compound of formula (I), wherein, X is N; Y is CH or N
  • A is:
  • R 1 is hydrogen;
  • R 2 is hydrogen;
  • R 3 is -CHF2 or CH2F;
  • R 71 , R 72 , R 73 and R 74 are independently of each other, selected from the group consisting of hy- drogen; Cl; F; Br; I; CN; methyl, ethynyl, propynyl.
  • the present invention provides an agrochemical mixture comprising at least one compound of formula (I) or in the form of a stereoisomer or an agriculturally accepta- ble salt or a tautomer or an isotopic form or a N-oxide or a S-oxide or a prodrug thereof, and at least one pesticidally active substance selected from the group consisting of herbicides, safen- ers, fungicides, insecticides and plant growth regulators.
  • the present invention provides a composition comprising at least one compound of formula (I), or in the form of a stereoisomer or an agriculturally acceptable salt or a tautomer or an isotopic form of a N-oxide or a S-oxide or a prodrug thereof, and an auxiliary.
  • the present invention provides a method for combating phytopatho genic harmful fungi, which process comprises treating the phytopathogenic fungi, the plant, or the plant propagation material selected from seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants to be protected against fungal attack, the stored materials or harvest, or alternately, the locus or soil or soil sub- stituents or surfaces therefrom, with an effective amount of at least one compound of formula (I), an agriculturally acceptable salt thereof or a tautomer or an isotopic form or a N-oxide or a S-oxide or a prodrug.
  • the present invention encompasses heteroaryl compounds of
  • X denotes CR 4 or N
  • Y denotes CR 5 or N
  • A is selected from the group consisting of:
  • R 4 is selected from the group consisting of hydrogen and halogen
  • R 5 is selected from the group consisting of hydrogen; halogen; CN; unsubstituted or sub- stituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted al- kynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloal kenyl; unsubstituted or substituted heterocycloalkyl and unsubstituted or substituted heterocycloalkenyl;
  • R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 and R 25 are inde- pendently of each other, selected from the group consisting of hydrogen; halogen; CN; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubsti- tuted or substituted alkynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substituted aryl; unsubstituted or substi- tuted -(alkylene)-aryl; unsubstituted or substituted heterocycloalkyl; unsubstituted or substituted heterocycloalkenyl; unsubstituted or substituted heteroary
  • R 14 is selected from the group consisting of halogen; CN; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; un- substituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsub- stituted or substituted aryl; unsubstituted or substituted -(alkylene)-aryl; unsubstituted or substituted heterocycloalkyl; unsubstituted or substituted heterocycloalkenyl; un- substituted or substituted heteroaryl;
  • R 17 together with R 18 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
  • R 19 together with R 20 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
  • R 21 together with R 22 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
  • R 115 and R 116 are independently of each other selected from the group consisting of H; halo- gen; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubsti- tuted or substituted alkynyl; unsubstituted or unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substituted heterocycloal- kyl; and unsubstituted or substituted heterocycloalkenyl;
  • the alkyl are straight-chain or branched, and comprise 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms as chain links;
  • alkenyl are straight-chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
  • alkynyl are straight-chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
  • heteroalkyl, heteroalkenyl and heteroalkynyl comprise 1, 2, 3, 4, 5 or 6 carbon atoms and 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from O, N(H) or S as chain links;
  • heterocycloalkyl and heterocycloalkenyl are 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from the group consisting of O, N(H) and S as ring members;
  • the aryl are mono-, bicyclic or tricyclic and comprise 6, 10 or 14 carbon atoms;
  • heteroaryl are mono- or bicyclic and 5- or 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently selected from the group consisting of O, N(H) or S as ring members;
  • a 0, 1, 2 or 3;
  • b 0, 1, 2 or 3;
  • c 0, 1, 2 or 3;
  • d 0, 1, 2 or 3;
  • e 0, 1, 2 or 3;
  • f 0, 1, 2 or 3;
  • g 0, 1, 2 or 3;
  • h is 1, 2 or 3;
  • i 1, 2 or 3;
  • j 0, 1, 2 or 3;
  • k 0, 1, 2 or 3;
  • l 0, 1, 2 or 3;
  • n 0, 1, 2 or 3;
  • n 0, 1, 2 or 3;
  • o 1, 2 or 3;
  • X denotes N and Y denotes CR 5 ;
  • X denotes CR 4 and Y denotes N;
  • X denotes N and Y denotes N;
  • A is as defined in the fifth embodiment
  • the present invention encompasses compounds, wherein the
  • compound of formula (I) is a compound of formula I(A),
  • X and Y are as defined in the fifth embodiment
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 25 , R 71 , R 72 , R 73 and R 74 , a, b, c, d, e, f, g, h, I, j, k, l, m, n and o are as defined in the fifth embodiment;
  • the present invention encompasses the compounds of formula I(A), wherein, X is CR 4 ; Y is CR 5 ; R 1 is hydrogen; R 2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2;
  • R 3 is selected from the group consisting of methyl, ethenyl, isopropenyl, ethynyl and cy- clopropyl; and the remaining of R 4 and R 5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; -CF3; -CHF2; -CH(F)-CF3; methyl, ethyl, propyl, butyl
  • R 3 and R 4 are independently of each other is selected from the group consisting of hydrogen; methyl, ethenyl, isopropenyl, ethynyl and cyclopropyl.
  • the compounds of formula (I) can be prepared by standard processes of organic chemistry.
  • the compounds of formula (I) can be prepared according to methods or in analogy to standard tech- niques that are described in the state of art.
  • the synthetic procedure utilises the starting materials that are either commercially available or that may be prepared according to conventional proce- dures starting from readily available compounds.
  • Reaction mixture was cooled to rt, diluted with ethyl acetate and filtered through celite. Organic layer was separated and washed with water, followed by washing with brine. Organic layer was separated, dried over Na 2 SO 4 and concentrated to afford crude product which was further purified by chromatography to afford the pure compound.
  • Individual compounds of formula I can also be prepared by derivatisation of other compounds of formula I or the intermediates thereof.
  • R 1 ; R 2 ; R 3 ; R 71 and R 72 are as in A.1. and R 5 ; R 73 and R 74 are as in B.3.
  • the compound of formula (I) is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • R 1 ; R 2 ; R 3 ; R 71 and R 72 are as in A.4. and R 5 ; R 73 and R 74 are as in B.59.
  • the compound of formula (I) is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • R 1 ; R 2 ; R 3 ; R 71 and R 72 are as in A.380. and R 5 ; R 73 and R 74 are as in B.19.
  • R 74 is H and R 73 is -CN.
  • the compound of formula (I) is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-phenyl
  • R 1 ; R 2 ; R 3 ; R 71 and R 72 are as in A.1. and R 73 and R 74 are as in C.3.
  • the compound of formula (I) is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • R 1 ; R 2 ; R 3 ; R 71 and R 72 are as in A.4. and R 73 and R 74 are as in C.59.
  • the compound of formula (I) is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • R 1 ; R 2 ; R 3 ; R 71 and R 72 are as in A.380. and R 73 and R 74 are as in C.19.
  • A, X, Y, R 1 , R 2 and R 3 are as defined in the first to forty nine embodiments hereinabove; comprises the reaction steps as outlined in Process scheme 1 and Process scheme 2 described below, wherein,
  • Step 1a Potassium iodide (KI), iodine (I) and N-iodosuccinimide; dimethyl formamide (DMF), methanol, ethanol and water; 2- 16 h; RT (room temperature);
  • Step 1b Tosyl chloride and tert-butoxycarbonyl anhydride; 2-16 h; 0°C;
  • Step 1c Tetrahydrofuran (THF) or DMF; Potassium carbonate (K2CO3) or Na2CO3) or their mix- ture; 2-14 h; 110°C
  • Step 1d Sodium hydride (NaH), Sodium methoxide (MeONa) and Sodium ethoxide (EtONa); 1 to 24 h; RT or 0°C to 90°C; comprises the reaction steps of:
  • This process step comprises reacting compound of formula 1-a (wherein A is defined as in twenty seventh to forty nineth embodiments) and R 1 is hydrogen; with a halogenating agent se- lected from the group consisting of KI, I and N-iodosuccinimide, in the presence of solvent se- lected from the group consisting of DMF, methanol, ethanol and water to obtain a compound of formula 1-a′.
  • Step 1b :
  • This process step comprises reacting the compound of formula 1-a′ with a reagent selected from the group consisting of tosyl chloride and tert-butoxycarbonyl anhydride to obtain a com- pound of formula 1-b.
  • a reagent selected from the group consisting of tosyl chloride and tert-butoxycarbonyl anhydride to obtain a com- pound of formula 1-b.
  • This process step comprises reacting the compound of formula 1-a with compound of for- mula 1-b in the presence of a polar solvent selected from the group consisting of THF and DMF and a base selected from the group consisting of K2CO3 and Na2CO3 to form a compound of formula (1-c′).
  • a polar solvent selected from the group consisting of THF and DMF
  • a base selected from the group consisting of K2CO3 and Na2CO3
  • This process step comprises reacting the compound of formula 1-c′ in the presence of a base selected from the group consisting of NaH, MeONa and EtONa to obtain a compound of formula (I); wherein R 1 is H; Step 1e:
  • This process step comprises reacting the compound of formula (I) obtained in step (1d) with an appropriate R1 in the presence of a suitable base; to obtain a compound of formula (I), wherein R 1 is as defined in the twenty seventh to forty nineth embodiment;
  • step (1d) or step (1e) is converted to its agri- culturally acceptable salts
  • Methanol (MeOH); ethanol (EtOH); and THF; 6-16h; heated to reflux; comprises the reaction steps of:
  • Step 2a This process step involves reacting compounds of formula 2 a with a compound of formula 2-b or compound of formula 2-c in the presence of a solvent selected from the group consisting of MeOH, EtOH, and THF and an acid selected from acetic acid, HCl, H 2 SO 4 , and trifluoroacetic acid to obtain a compound of formula (I) or to obtain an intermediate of formula I-a.
  • the intermediate is further treated with an acid selected from the group con- sisting of HCl, H 2 SO 4 , AcOH and THFto obtain a compound of formula (I).
  • the compounds according to the invention may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers.
  • the invention provides both the single pure enantiomers or pure diastereomers of the compounds according to the invention, and their mixtures and the use according to the invention of the pure enantiomers or pure diastereomers of the compounds according to the in- vention or their mixtures.
  • Suitable compounds according to the invention also include all possible geometrical stereoisomers (cis/trans isomers) and mixtures thereof. Cis/trans isomers may be present with respect to an alkene, carbon-nitrogen double-bond or amide group.
  • ste- reoisomer(s) encompasses both optical isomers, such as enantiomers or diastereomers, the lat- ter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis/trans isomers).
  • the present invention relates to every possible stereoisomer of the com- pounds of formula I, i.e. to single enantiomers or diastereomers, as well as to mixtures thereof.
  • the compounds of formula (I) may be amorphous or may exist in one or more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities.
  • the present invention relates to amor- phous and crystalline compounds of formula I, mixtures of different crystalline states of the re- spective compound I, as well as amorphous or crystalline salts thereof.
  • Salts of the compounds of the formula (I) are preferably agriculturally acceptable salts. They can be formed in a customary manner, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality. Agriculturally useful salts of the compounds of formula I encompass especially the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the mode of action of the compounds of formula I.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydro- gensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can preferably be formed by reacting compounds of formula I with an acid of the corresponding anion, preferably of hydrochlo- ric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • the present invention relates to agricultural mixtures as defined herein comprising at least one of the compounds as defined in any one of the embodiments from first embodiment to the forty nineth embodiment.
  • the pre- sent invention relates to compositions as defined herein comprising at least one of the any one of the embodiments from first embodiment to the forty nineth embodiments.
  • the present invention relates to the methods as defined herein comprising the application of any one of the compounds as defined in any one of the embodiments any one of the embodiments from first embodiment to the forty nineth embodiment
  • the compounds of the formula (I) or compositions comprising said compounds according to the invention and the mixtures comprising said compounds and compositions, respectively, are suitable as agrochemical fungicides.
  • phytopatho- genic fungi which derive especially from the following classes or are closely related to any of them: Solani, for example, but not limited to the genus Alternaria; fusarium or Rhizoctonia; Soro- kiniana, for example, but not limited to the genus Bipolaris; Cinerea, for example, not limited to Botyris; Miyabeanus, not limited to Cochliobolus; Orbiculare, not limited to Colletotrichum; Teres, but not limited to Drechslera or Pyrenophora ; Repentis, but not limited to Tritici; Erysiphe spp.
  • Culmorum but not limited to Fusarium; Nivale, but not limited to Microdochium; Monilinia spp. e. g. M. laxa, M. fructicola and M. fructigena; Oryzae, but not limited to Bipolaris, Entyloma, Hem- ileia, Pyricularia and Rocladium; Pachyrhizi, but not limited to Phakopspora; Sclerotiorium, but not limited to Sclerotinia; Tritici, but not limited to Zymoseptoria; Basicola, but not limited to Thielaviopsis; Maydis, but not limited to Ustilago.
  • the compounds of formula (I) further show phytopathogenic activity against pathogens that are resistant to complex 2 or complex 3 respiratory chain inhibitors e.g: in Sclerotinia sclerotiorum and/or Botyris cinerea.
  • Some of the compounds of the formula I and the compositions according to the invention are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
  • the compounds I and the compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g.
  • leguminous plants such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, toma- toes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, sugar cane or oil palm; corn; to- bacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf
  • compounds I and compositions thereof are used for controlling a multi- tude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamen- tals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • field crops such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamen- tals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • plant propagation material is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pour ing.
  • treatment of plant propagation materials with compounds I and compositions thereof, respectively is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
  • cultiva plants is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://cera-gmc.org/, see GM crop database therein).
  • Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be ob- tained by cross breeding, mutations or natural recombination.
  • one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.
  • Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by glycosylation or poly- mer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
  • herbicides e. bromoxynil or ioxynil herbicides as a result of conventional meth- ods of breeding or genetic engineering. Furthermore, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glypho- sate and glufosinate or to both glyphosate and a herbicide from another class such as ALS inhib- itors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors. These herbicide resistance tech- nologies are e. g. described in Pest Managem.
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as ⁇ -endotoxins, e. g. CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1, VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp.
  • VIP1 vegetative insecticidal proteins
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins, or other insect specific neurotoxins
  • toxins produced by fungi such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins
  • proteinase inhibi- tors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-trans- ferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase
  • ion channel blockers such as blockers of sodium or
  • these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins.
  • Hybrid proteins are characterized by a new combination of protein domains, (see, e. g. WO 02/015701).
  • Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, e. g., in EP-A 374753, WO 93/007278, WO 95/34656, EP-A 427529, EP-A 451878, WO 03/18810 und WO 03/52073.
  • the methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above.
  • insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of arthropods, especially to beetles (Coeloptera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda).
  • Genetically modified plants capable to synthesize one or more insecticidal proteins are, e.
  • WO 03/018810 MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a mod- ified version of the Cry1Ac toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1F toxin and PAT enzyme).
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bac- terial, viral or fungal pathogens.
  • proteins are the so-called“pathogenesis-re- lated proteins” (PR proteins, see, e. g. EP-A 392225), plant disease resistance genes (e. g. po- tato cultivars, which express resistance genes acting against Phytophthora infestans derived from the Mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amyl- vora).
  • PR proteins so-called“pathogenesis-re- lated proteins”
  • plant disease resistance genes e. g. po- tato cultivars, which express resistance genes acting against Phytophthora infestans derived from the Mexican wild potato Solanum bulbocast
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth- limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
  • productivity e. g. bio mass production, grain yield, starch content, oil content or protein content
  • plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g. oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera ® rape, DOW Agro Sciences, Canada). Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Am- flora ® potato, BASF SE, Germany).
  • recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g. oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera ® rape, DOW Agro Sciences, Canada).
  • the compounds of formula (I) and compositions thereof, respectively, are particularly suitable for controlling the following plant diseases:
  • Albugo spp. white rust on ornamentals, vegetables (e. g. A. candida) and sunflowers (e. g. A. tragopogonis); Alternaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassicola or brassi- cae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A. alternata), to- matoes (e. g. A. solani or A. alternata) and wheat; Aphanomyces spp. on sugar beets and vege- tables; Ascochyta spp. on cereals and vegetables, e. g. A.
  • Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn (e. g.
  • Gray leaf spot C. zeae-maydis
  • rice sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice
  • Cladosporium spp. on tomatoes e. g. C. fulvum: leaf mold
  • cereals e. g. C. herbarum (black ear) on wheat
  • Cochliobolus anamorph: Helminthosporium of Bipolaris
  • spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C.
  • sativus anamorph: B. sorokiniana
  • rice e. g. C. miyabeanus, anamorph: H. oryzae
  • Colletotrichum teleomorph: Glomerella
  • spp. anthracnose on cotton (e. g. C. gossypii), corn (e. g. C. graminicola: Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemuthianum) and soybeans (e. g. C. truncatum or C. gloeosporioides); Corticium spp., e. g. C. C.
  • sasakii sheath blight
  • Corynespora cas- siicola leaf spots
  • Cycloconium spp. e. g. C. oleaginum on olive trees
  • Cylindrocarpon spp. e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.
  • liriodendri Neonectria liriodendri: Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. D.
  • tritici-repentis tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeo moniella chlamydospora (earlier Phaeoacremonium chlamydosporum), Phaeoacremonium ale- ophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta: anthracnose) and vines (E.
  • ampelina anthracnose
  • Entyloma oryzae leaf smut
  • Epicoc- cum spp. black mold
  • Erysiphe spp. potowdery mildew
  • sugar beets E. betae
  • vegetables e. g. E. pisi
  • cucurbits e. g. E. cichoracearum
  • cabbages e. g. E. cruciferarum
  • Eutypa lata Eutypa canker or dieback, anamorph: Cytosporina lata, syn.
  • G. sabinae rust on pears
  • Helminthosporium spp. syn. Drechslera, teleomorph: Cochliobolus
  • Hemileia spp. e. g. H. vastatrix (coffee leaf rust) on coffee
  • Isariopsis clavispora syn. Cladosporium vitis
  • Macropho- mina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton
  • Microdochium syn. Fusarium) nivale (pink snow mold) on cereals (e. g.
  • Microsphaera diffusa (pow- dery mildew) on soybeans
  • Monilinia spp. e. g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants
  • Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas
  • Peronospora spp. (downy mildew) on cabbage (e. g. P.
  • brassicae brassicae
  • rape e. g. P. parasitica
  • onions e. g. P. destructor
  • tobacco P. tabacina
  • soybeans e. g. P. manshurica
  • Phakopsora pachyrhizi and P. meibomiae silkbean rust
  • Phialophora spp. e. g. on vines (e. g. P. tra- cheiphila and P. tetraspora) and soybeans (e. g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P.
  • betae root rot, leaf spot and damping-off on sugar beets
  • Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e. g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P.
  • infestans late blight
  • broad-leaved trees e. g. P. ramorum: sudden oak death
  • Plasmodiophora brassicae club root
  • Plasmo- para spp. e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers
  • Podosphaera spp. powdery mildew) on rosaceous plants, hop, pome and soft fruits, e. g. P. leu- cotricha on apples
  • Polymyxa spp. e. g. on cereals, such as barley and wheat (P.
  • Pseudocercosporella herpotrich- oides eyespot, teleomorph: Tapesia yallundae
  • Pseudoperono- spora downy mildew
  • Pseu- dopezicula tracheiphila red fire disease or ⁇ rotbrenner’, anamorph: Phialophora
  • Puc- cinia spp. rusts
  • oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum); Ramularia spp., e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp.
  • R. solani root and stem rot
  • S. solani silk and stem rot
  • S. solani silk and stem rot
  • S. solani silk blight
  • R. cerealis Rhizoctonia spring blight
  • Rhizopus stolonifer black mold, soft rot
  • Rhynchosporium secalis scald
  • seed rot or white mold on vegetables and field crops, such as rape, sunflowers (e. g. S. sclero- tiorum) and soybeans (e. g. S. rolfsii or S. sclerotiorum); Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagono- spora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn.
  • Erysiphe necator prowdery mildew, anamorph: Oidium tuckeri
  • Setospaeria spp. leaf blight
  • corn e. g. S. turci- cum, syn. Helminthosporium turcicum
  • turf e. g. S.
  • deformans leaf curl disease
  • T. pruni plum pocket
  • plums Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stink- ing smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U.
  • occulta stem smut
  • Uromyces spp. rust
  • vegetables such as beans (e. g. U. appen- diculatus, syn. U. phaseoli) and sugar beets (e. g. U. betae)
  • Ustilago spp. loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis: corn smut) and sugar cane
  • Venturia spp. scab
  • apples e. g. V. inaequalis
  • pears Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae on strawberries, rape, potatoes and tomatoes.
  • the compounds I and compositions thereof, respectively, are particu- larly suitable for controlling the following plant diseases: Puccinia spp. (rusts) on various plants, for example, but not limited to P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye and Phakopsoraceae spp. on various plants, in partic- ular Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans.
  • Puccinia spp. rusts
  • rusts rusts
  • P. triticina brown or leaf rust
  • P. striiformis stripe or yellow rust
  • the compounds I and compositions thereof, respectively, are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials.
  • protection of materials is to be understood to denote the protection of technical and non-living materials, such as adhesives, glues, wood, paper and paperboard, textiles, leather, paint dispersions, plastics, cooling lubricants, fiber or fabrics, against the infestation and destruc tion by harmful microorganisms, such as fungi and bacteria.
  • Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaeto- mium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp.
  • Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaeto- mium spp., Humicola spp., Petriella spp., Trichurus spp.
  • Basidiomycetes such as Coniophora
  • yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.
  • the method of treatment according to the invention can also be used in the field of protecting stored products or harvest against attack of fungi and microorganisms.
  • the term "stored products” is understood to denote natural substances of plant or animal origin and their processed forms, which have been taken from the natural life cycle and for which long-term protection is desired.
  • Stored products of crop plant origin such as plants or parts thereof, for example stalks, leafs, tubers, seeds, fruits or grains, can be protected in the freshly harvested state or in processed form, such as pre-dried, moistened, comminuted, ground, pressed or roasted, which process is also known as post-harvest treatment.
  • stored products are timber, whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood.
  • Stored products of animal origin are hides, leather, furs, hairs and the like.
  • the combinations according the present invention can prevent disadvantageous effects such as de- cay, discoloration or mold.
  • Preferably "stored products” is understood to denote natural sub- stances of plant origin and their processed forms, more preferably fruits and their processed forms, such as pomes, stone fruits, soft fruits and citrus fruits and their processed forms.
  • the compounds of formula I can be present in different crystal modifications whose biological activity may differ. They are likewise subject matter of the present invention.
  • the compounds I are employed as such or in form of compositions by treating the fungi or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be pro- tected from fungal attack with a fungicidally effective amount of the active substances.
  • the appli- cation can be carried out both before and after the infection of the plants, plant propagation ma- terials, such as seeds, soil, surfaces, materials or rooms by the fungi.
  • Plant propagation materials may be treated with compounds I as such or a composition compris- ing at least one compound I prophylactically either at or before planting or transplanting.
  • the invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I according to the invention.
  • An agrochemical composition comprises a fungicidally effective amount of a compound I.
  • the term "effective amount” denotes an amount of the composition or of the compounds I, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound I used.
  • the compounds (I), their N-oxides and salts can be converted into customary types of agrochem- ical compositions, e. g.
  • composition types are suspensions (e. g. SC, OD, FS), emulsifiable concentrates (e. g. EC), emulsions (e. g. EW, EO, ES, ME), capsules (e. g. CS, ZC), pastes, pastilles, wettable powders or dusts (e. g. WP, SP, WS, DP, DS), pressings (e. g. BR, TB, DT), granules (e. g.
  • compositions types are defined in the“Catalogue of pesticide formulation types and international coding system”, Technical Monograph No.2, 6 th Ed. May 2008, CropLife Inter- national.
  • compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bac- tericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e. g. kerosene, diesel oil; oils of vegetable or animal origin; ali- phatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e. g. ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, e. g. cyclohexanone; esters, e. g.
  • mineral oil fractions of medium to high boiling point e. g. kerosene, diesel oil
  • oils of vegetable or animal origin oils of vegetable or animal origin
  • ali- phatic, cyclic and aromatic hydrocarbons e. g. toluene, paraffin, tetrahydronaphthal
  • lactates carbonates, fatty acid esters, gamma- butyrolactone; fatty acids; phosphonates; amines; amides, e. g. N-methyl pyrrolidone, fatty acid dimethyl amides; and mixtures thereof.
  • Suitable solid carriers or fillers are mineral earths, e. g. silicates, silica gels, talc, kaolins, lime- stone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e. g. cellulose, starch; fertilizers, e. g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e. g. ce- real meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • mineral earths e. g. silicates, silica gels, talc, kaolins, lime- stone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide
  • polysaccharides e.
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and am- photeric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon’s, Vol.1: Emulsifiers & Detergents, McCutcheon’s Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylaryl sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of con- densed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkyl naphthalenes, sulfosuccinates or sulfosuccinamates.
  • Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, es- ters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkox- ylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • N- substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar-based surfac- tants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides.
  • polymeric surfactants are home- or copolymers of vinyl pyrrolidone, vinyl alcohols, or vinyl acetate.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium com- pounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable am- photeric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block poly- mers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinyl amines or polyethylene amines.
  • Suitable adjuvants are compounds, which have a negligible or even no pesticidal activity them- selves, and which improve the biological performance of the compound I on the target.
  • examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e. g. xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants are pigments of low water solubility and water- soluble dyes.
  • examples are inorganic colorants (e. g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e. g. alizarin-, azo- and phthalocyanine colorants).
  • Suitable tackifiers or binders are polyvinyl pyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers. Examples for composition types and their preparation are:
  • a compound I and 5-15 wt% wetting agent e. g. alcohol alkoxylates
  • a water-soluble solvent e. g. alcohols
  • a compound I and 1-10 wt% dispersant e. g. polyvinyl pyrrolidone
  • organic solvent e. g. cyclohexanone
  • emulsifiers e. g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • water-insoluble organic solvent e. g. aromatic hydro- carbon
  • Emulsions EW, EO, ES
  • emulsifiers e. g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • 20-40 wt% water-insoluble organic solvent e. g. aromatic hydrocarbon
  • This mixture is introduced into water ad 100 wt% by means of an emulsifying ma- chine and made into a homogeneous emulsion. Dilution with water gives an emulsion.
  • a compound I In an agitated ball mill, 20-60 wt% of a compound I are comminuted with addition of 2-10 wt% dispersants and wetting agents (e. g. sodium lignosulfonate and alcohol ethoxylate), 0.1-2 wt% thickener (e. g. xanthan gum) and water ad 100 wt% to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt% binder (e. g. polyvinyl alcohol) is added.
  • dispersants and wetting agents e. g. sodium lignosulfonate and alcohol ethoxylate
  • 0.1-2 wt% thickener e. g. xanthan gum
  • a compound I 50-80 wt% of a compound I are ground finely with addition of dispersants and wetting agents (e. g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt% and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants and wetting agents e. g. sodium lignosulfonate and alcohol ethoxylate
  • wt% of a compound I are ground in a rotor-stator mill with addition of 1-5 wt% dispersants (e. g. sodium lignosulfonate), 1-3 wt% wetting agents (e. g. alcohol ethoxylate) and solid carrier (e. g. silica gel) ad 100 wt%. Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants e. g. sodium lignosulfonate
  • wetting agents e. g. alcohol ethoxylate
  • solid carrier e. g. silica gel
  • a compound I In an agitated ball mill, 5-25 wt% of a compound I are comminuted with addition of 3-10 wt% dispersants (e. g. sodium lignosulfonate), 1-5 wt% thickener (e. g. carboxymethyl cellulose) and water ad 100 wt% to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
  • dispersants e. g. sodium lignosulfonate
  • 1-5 wt% thickener e. g. carboxymethyl cellulose
  • wt% of a compound I are added to 5-30 wt% organic solvent blend (e. g. fatty acid dimethyl amide and cyclohexanone), 10-25 wt% surfactant blend (e. g. alcohol ethoxylate and arylphenol ethoxylate), and water ad 100 %. This mixture is stirred for 1 h to produce spontaneously a ther- modynamically stable microemulsion.
  • organic solvent blend e. g. fatty acid dimethyl amide and cyclohexanone
  • surfactant blend e. g. alcohol ethoxylate and arylphenol ethoxylate
  • An oil phase comprising 5-50 wt% of a compound I, 0-40 wt% water insoluble organic solvent (e. g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e. g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e. g. poly- vinyl alcohol). Radical polymerization results in the formation of poly(meth)acrylate microcap- sules.
  • an oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e. g. aromatic hydrocarbon), and an isocyanate mon- omer (e. g.
  • diphenylmethene-4,4’-diisocyanatae are dispersed into an aqueous solution of a pro- tective colloid (e. g. polyvinyl alcohol).
  • a pro- tective colloid e. g. polyvinyl alcohol.
  • the addition of a polyamine results in the formation of polyurea microcapsules.
  • the monomers amount to 1-10 wt%.
  • the wt% relate to the total CS composition.
  • Dustable powders (DP, DS)
  • a compound I 0.5-30 wt% of a compound I is ground finely and associated with solid carrier (e. g. silicate) ad 100 wt%.
  • solid carrier e. g. silicate
  • Granulation is achieved by extrusion, spray-drying or fluidized bed.
  • organic solvent e. g. aromatic hydrocarbon
  • compositions types i) to xiii) may optionally comprise further auxiliaries, such as 0.1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1-1 wt% anti-foaming agents, and 0.1-1 wt% col- orants.
  • the agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, more preferably between 1 and 70%, and in particular between 10 and 60%, by weight of active substance.
  • the active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • solutions for seed treatment (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emul- sions (ES), emulsifiable concentrates (EC), and gels (GF) are usually employed.
  • the composi- tions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Application can be carried out before or during sowing.
  • Methods for applying compound I and compositions thereof, respectively, onto plant propagation material, especially seeds include dressing, coating, pelleting, dusting, and soaking as well as in-furrow application methods.
  • compound I or the compositions thereof, respectively are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dust- ing.
  • the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.
  • amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propa- gation material (preferably seeds) are generally required.
  • the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
  • oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix).
  • pesticides e. g. herbicides, insecticides, fungicides, growth regulators, safeners, biopesticides
  • These agents can be admixed with the compositions accord- ing to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.
  • a pesticide is generally a chemical or biological agent (such as pestidal active ingredient, com pound, composition, virus, bacterium, antimicrobial or disinfectant) that through its effect deters, incapacitates, kills or otherwise discourages pests.
  • Target pests can include insects, plant path- ogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microbes that de- stroy property, cause nuisance, spread disease or are vectors for disease.
  • pesticide includes also plant growth regulators that alter the expected growth, flowering, or reproduction rate of plants; defoliants that cause leaves or other foliage to drop from a plant, usually to facilitate harvest; desiccants that promote drying of living tissues, such as unwanted plant tops; plant acti- vators that activate plant physiology for defense of against certain pests; safeners that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology e.g. to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.
  • the user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained.
  • 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to- use spray liquor are applied per hectare of agricultural useful area.
  • individual components of the composition according to the inven- tion such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
  • a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
  • one embodiment of the invention is a kit for preparing a usable pesticidal compo- sition, the kit comprising a) a composition comprising component 1) as defined herein and at least one auxiliary; and b) a composition comprising component 2) as defined herein and at least one auxiliary; and optionally c) a composition comprising at least one auxiliary and optionally a further active component 3) as defined herein.
  • pesticides II e. g. pesticidally-active substances and biopesticides
  • con- junction with which the compounds I can be used is intended to illustrate the possible combina- tions but does not limit them:
  • Respiration inhibitors Inhibitors of complex III at Qo site: azoxystrobin (A.1.1), coumeth- oxystrobin (A.1.2), coumoxystrobin (A.1.3), dimoxystrobin (A.1.4), enestroburin (A.1.5), fenamin- strobin (A.1.6), fenoxystrobin/flufenoxystrobin (A.1.7), fluoxastrobin (A.1.8), kresoxim-methyl (A.1.9), mandestrobin (A.1.10), metominostrobin (A.1.11), orysastrobin (A.1.12), picoxystrobin (A.1.13), pyraclostrobin (A.1.14), pyrametostrobin (A.1.15), pyraoxystrobin (A.1.16), trifloxy- strobin (A.1.17), 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxy
  • Inhibitors of complex III at Q i site cyazofamid (A.2.1), amisulbrom (A.2.2), [(6S,7R,8R)-8-benzyl- 3-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] 2- methylpropanoate (A.2.3), [2-[[(7R,8R,9S)-7-benzyl-9-methyl-8-(2-methylpropanoyloxy)-2,6-di- oxo-1,5-dioxonan-3-yl]carbamoyl]-4-methoxy-3-pyridyl]oxymethyl 2-methylpropanoate (A.2.4), [(6S,7R,8R)-8-benzyl-3-[[4-methoxy-3-(propanoyloxymethoxy)pyridine-2-carbonyl]amino
  • Inhibitors of complex II benodanil (A.3.1), benzovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapyroxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.11), isopyrazam (A.3.12), mepronil (A.3.13), oxycar- boxin (A.3.14), penflufen (A.3.15), penthiopyrad (A.3.16), 3-(difluoromethyl)-N-methoxy-1-methyl- N-[1-methyl-2-(2,4,6-trichlorophenyl)ethyl]pyrazole-4-carboxamide (A.3.17), N-[2-(3,4-difluoro- phenyl)phenyl]-3-(
  • respiration inhibitors diflumetorim (A.4.1); nitrophenyl derivates: binapacryl (A.4.2), dino- buton (A.4.3), dinocap (A.4.4), fluazinam (A.4.5), meptyldinocap (A.4.6), ferimzone (A.4.7); or- ganometal compounds: fentin salts, e. g. fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.11); silthiofam (A.4.12).
  • fentin salts e. g. fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10)
  • ametoctradin A.4.11
  • silthiofam A.4.12).
  • C14 demethylase inhibitors triazoles: azaconazole (B.1.1), bitertanol (B.1.2), bromuconazole (B.1.3), cyproconazole (B.1.4), difenoconazole (B.1.5), diniconazole (B.1.6), diniconazole-M (B.1.7), epoxiconazole (B.1.8), fenbuconazole (B.1.9), fluquinconazole (B.1.10), flusilazole (B.1.11), flutriafol (B.1.12), hexaconazole (B.1.13), imibenconazole (B.1.14), ipconazole (B.1.15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1.19), paclobutrazole (B.1.20), penconazole (B.1.21), propiconazole (B.1.22)
  • Delta14-reductase inhibitors aldimorph (B.2.1), dodemorph (B.2.2), dodemorph-acetate (B.2.3), fenpropimorph (B.2.4), tridemorph (B.2.5), fenpropidin (B.2.6), piperalin (B.2.7), spiroxamine (B.2.8).
  • Inhibitors of 3-keto reductase fenhexamid (B.3.1).
  • Phenylamides or acyl amino acid fungicides benalaxyl (C.1.1), benalaxyl-M (C.1.2), kiralaxyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (C.1.5), ofurace (C.1.6), oxadixyl (C.1.7).
  • nucleic acid synthesis inhibitors hymexazole (C.2.1), octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine (C.2.6), 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine (C.2.7), 5-fluoro-2-(4-chlorophenyl- methoxy)pyrimidin-4 amine (C.2.8).
  • D) Inhibitors of cell division and cytoskeleton Tubulin inhibitors benomyl (D.1.1), carbendazim (D.1.2), fuberidazole (D1.3), thiabendazole (D.1.4), thiophanate-methyl (D.1.5), 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine (D.1.6), 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine (D.1.7), N-ethyl-2-[(3- ethynyl-8-methyl-6-quinolyl)oxy]butanamide (D.1.8), N-ethyl-2-[(3-ethynyl-8-methyl- 6-quinolyl)oxy]-2-methylsulfanyl-acetamide (D.1.9), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-
  • diethofencarb (D.2.1), ethaboxam (D.2.2), pencycuron (D.2.3), fluopicolide (D.2.4), zoxamide (D.2.5), metrafenone (D.2.6), pyriofenone (D.2.7).
  • Methionine synthesis inhibitors cyprodinil (E.1.1), mepanipyrim (E.1.2), pyrimethanil (E.1.3). Protein synthesis inhibitors: blasticidin-S (E.2.1), kasugamycin (E.2.2), kasugamycin hydrochlo- ride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6).
  • MAP / histidine kinase inhibitors fluoroimid (F.1.1), iprodione (F.1.2), procymidone (F.1.3), vin- clozolin (F.1.4), fludioxonil (F.1.5).
  • G protein inhibitors quinoxyfen (F.2.1).
  • Phospholipid biosynthesis inhibitors edifenphos (G.1.1), iprobenfos (G.1.2), pyrazophos (G.1.3), isoprothiolane (G.1.4).
  • Lipid peroxidation dicloran (G.2.1), quintozene (G.2.2), tecnazene (G.2.3), tolclofos-methyl (G.2.4), biphenyl (G.2.5), chloroneb (G.2.6), etridiazole (G.2.7).
  • Phospholipid biosynthesis and cell wall deposition dimethomorph (G.3.1), flumorph (G.3.2), man- dipropamid (G.3.3), pyrimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7).
  • Inhibitors of oxysterol binding protein oxathiapiprolin (G.5.1), 2- ⁇ 3-[2-(1- ⁇ [3,5-bis(difluoromethyl- 1H-pyrazol-1-yl]acetyl ⁇ piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl ⁇ phenyl me- thanesulfonate (G.5.2), 2- ⁇ 3-[2-(1- ⁇ [3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl ⁇ piperidin-4-yl) 1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl ⁇ -3-chlorophenyl methanesulfonate (G.5.3), 4-[1-[2- [3-(difluoromethyl)-5-methyl-pyrazol-1-yl]acetyl]-4-pipe
  • Inorganic active substances Bordeaux mixture (H.1.1), copper (H.1.2), copper acetate (H.1.3), copper hydroxide (H.1.4), copper oxychloride (H.1.5), basic copper sulfate (H.1.6), sulfur (H.1.7).
  • Thio- and dithiocarbamates ferbam (H.2.1), mancozeb (H.2.2), maneb (H.2.3), metam (H.2.4), metiram (H.2.5), propineb (H.2.6), thiram (H.2.7), zineb (H.2.8), ziram (H.2.9).
  • Organochlorine compounds anilazine (H.3.1), chlorothalonil (H.3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorphenole (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.11).
  • Guanidines and others guanidine (H.4.1), dodine (H.4.2), dodine free base (H.4.3), guazatine (H.4.4), guazatine-acetate (H.4.5), iminoctadine (H.4.6), iminoctadine-triacetate (H.4.7), iminoctadine-tris(albesilate) (H.4.8), dithianon (H.4.9), 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6- c']dipyrrole-1,3,5,7(2H,6H)-tetraone (H.4.10).
  • Inhibitors of glucan synthesis validamycin (I.1.1), polyoxin B (I.1.2).
  • Bronopol (K.1.1), chinomethionat (K.1.2), cyflufenamid (K.1.3), cymoxanil (K.1.4), dazomet (K.1.5), debacarb (K.1.6), diclocymet (K.1.7), diclomezine (K.1.8), difenzoquat (K.1.9), difen- zoquat-methylsulfate (K.1.10), diphenylamin (K.1.11), fenitropan (K.1.12), fenpyrazamine (K.1.13), flumetover (K.1.14), flusulfamide (K.1.15), flutianil (K.1.16), harpin (K.1.17), methasul- focarb (K.1.18), nitrapyrin (K.1.19), nitrothal-isopropyl (K.1.20), tolprocarb (K.1.21), oxin-copper (K.1.22), proqui
  • abscisic acid (M.1.1), amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat, chlormequat chloride, choline chloride, cyclanilide, daminozide, dikegulac, dime- thipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibber- ellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat, mepiquat chloride, naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione, prohexadi- one-calcium, prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate
  • N.1 Lipid biosynthesis inhibitors alloxydim (N.1.1), alloxydim-sodium (N.1.2), butroxydim (N.1.3), clethodim (N.1.4), clodinafop (N.1.5), clodinafop-propargyl (N.1.6), cycloxydim (N.1.7), cyhalofop (N.1.8), cyhalofop-butyl (N.1.9), diclofop(N.1.10), diclofop-methyl (N.1.11), fenoxaprop (N.1.12), fenoxaprop-ethyl (N.1.13), fenoxaprop-P (N.1.14), fenoxaprop-P-ethyl (N.1.15), fluazifop (N.1.16), fluazifop-butyl (N.1.17), fluazifop-P (N.1.18), fluazifop-
  • N.2 ALS inhibitors amidosulfuron (N.2.1), azimsulfuron (N.2.2), bensulfuron (N.2.3), bensulfuron- methyl (N.2.4), chlorimuron (N.2.5), chlorimuron-ethyl (N.2.6), chlorsulfuron (N.2.7), cinosulfuron (N.2.8), cyclosulfamuron (N.2.9), ethametsulfuron (N.2.10), ethametsulfuron-methyl (N.2.11), eth- oxysulfuron (N.2.12), flazasulfuron (N.2.13), flucetosulfuron (N.2.14), flupyrsulfuron (N.2.15), flupyrsulfuron-methyl-sodium (N.2.16), foramsulfuron (N.2.17), halosulfuron (N.2.18), halosulfu- ron-methyl (N.2.19),
  • N.3 Photosynthesis inhibitors amicarbazone (N.3.1); chlorotriazine (N.3.2); ametryn (N.3.3), at- razine (N.3.4), chloridazone (N.3.5), cyanazine (N.3.6), desmetryn (N.3.7), dimethametryn (N.3.8),hexazinone (N.3.9), metribuzin (N.3.10), prometon (N.3.11), prometryn (N.3.12), pro- pazine (N.3.13), simazine (N.3.14), simetryn (N.3.15), terbumeton (N.3.16), terbuthylazin (N.3.17), terbutryn (N.3.18), trietazin (N.3.19); chlorobromuron (N.3.20), chlorotoluron (N.3.21), chloroxuron (N.3.22), dimefuron (N.3.23), diuron (N.3.24), fluometuron
  • N.5 Bleacher herbicides beflubutamid (N.5.1), diflufenican (N.5.2), fluridone (N.5.3), flurochlo- ridone (N.5.4), flurtamone (N.5.5), norflurazon (N.5.6), picolinafen (N.5.7), 4-(3-trifluorome- thyl ⁇ phenoxy)-2-(4-trifluoromethylphenyl) ⁇ pyrimidine ((N.5.8) CAS 180608-33-7); benzobicyclon (N.5.9), benzofenap (N.5.10), bicyclopyrone (N.5.11), clomazone (N.5.12), fenquintrione (N.5.13), isoxaflutole (N.5.14), mesotrione (N.5.15), pyrasulfotole (N.5.16), pyrazolynate (N.5.17), pyrazoxyfen (N.5.18), sulcotrione
  • Glutamine synthase inhibitors bilanaphos (bialaphos) (N.7.1), bilanaphos-sodium (N.7.2), glufosinate (N.7.3), glufosinate-P (N.7.4), glufosinate-ammonium (N.7.5);
  • DHP synthase inhibitors asulam (N.8.1);
  • Mitosis inhibitors benfluralin (N.9.1), butralin (N.9.2), dinitramine (N.9.3), ethalfluralin (N.9.4), fluchloralin (N.9.5), oryzalin (N.9.6), pendimethalin (N.9.7), prodiamine (N.9.8), trifluralin (N.9.9); amiprophos (N.9.10), amiprophos-methyl (N.9.11), butamiphos (N.9.12); chlorthal (N.9.13), chlor- thal-dimethyl (N.9.14), dithiopyr (N.9.15), thiazopyr (N.9.16), propyzamide (N.9.17), tebutam (N.9.18); carbetamide (N.9.19), chlorpropham (N.9.20), flamprop (N.9.21), flamprop-isopropyl (N.9.22), flamprop-methyl (N.9.23), flamin (N
  • N.11 Cellulose biosynthesis inhibitors chlorthiamid (N.11.1), dichlobenil (N.11.2), flupoxam (N.11.3), indaziflam (N.11.4), isoxaben (N.11.5), triaziflam (N.11.6), 1-cyclohexyl-5-pentafluor- phenyloxy-14-[1,2,4,6]thiatriazin-3-ylamine ((N.11.7) CAS 175899-01-1);
  • N.12 Decoupler herbicides dinoseb (N.12.1), dinoterb (N.12.2), DNOC (N.12.3) and its salts; N.13 Auxinic herbicides: 2,4-D (N.13.1) and its salts and esters, clacyfos (N.13.2), 2,4-DB (N.13.3) and its salts and esters, aminocyclopyrachlor (N.13.4) and its salts and esters, amino- pyralid (N.13.5) and its salts such as aminopyralid-dimethylammonium (N.13.6), aminopyralid- tris(2-hydroxypropyl)ammonium (N.13.7) and its esters, benazolin (N.13.8), benazolin-ethyl (N.13.9), chloramben (N.13.10) and its salts and esters, clomeprop (N.13.11), clopyralid (N.13.
  • N.14 Auxin transport inhibitors diflufenzopyr (N.14.1), diflufenzopyr-sodium (N.14.2), naptalam (N.14.3) and naptalam-sodium (N.14.4);
  • N.15 Other herbicides: bromobutide (N.15.1), chlorflurenol (N.15.2), chlorflurenol-methyl (N.15.3), cinmethylin (N.15.4), cumyluron (N.15.5), cyclopyrimorate ((N.15.6) CAS 499223-49-3) and its salts and esters, dalapon (N.15.7), dazomet (N.15.8), difenzoquat (N.15.9), difenzoquat- metilsulfate (N.15.10), dimethipin (N.15.11), DSMA (N.15.12), dymron (N.15.13), endothal (N.15.14) and its salts, etobenzanid (N.15.15), flurenol (N.15.16), flurenol-butyl (N.15.17), flur- primidol (N.
  • Acetylcholine esterase (AChE) inhibitors aldicarb (O.1.1), alanycarb (O.1.2), bendiocarb (O.1.3), benfuracarb (O.1.4), butocarboxim (O.1.5), butoxycarboxim (O.1.6), carbaryl (O.1.7), car- bofuran (O.1.8), carbosulfan (O.1.9), ethiofencarb (O.1.10), fenobucarb (O.1.11), formetanate (O.1.12), furathiocarb (O.1.13), isoprocarb (O.1.14), methiocarb (O.1.15), methomyl (O.1.16), metolcarb (O.1.17), oxamyl (O.1.18), pirimicarb (O.1.19), propoxur (O.1.20), thiodicarb (O.1.21), thiofanox (O.1.22), trime
  • O.2 GABA-gated chloride channel antagonists endosulfan (O.2.1), chlordane (O.2.2); ethiprole (O.2.3), fipronil (O.2.4), flufiprole (O.2.5), pyrafluprole (O.2.6), pyriprole (O.2.7);
  • O.3 Sodium channel modulators acrinathrin (O.3.1), allethrin (O.3.2), d-cis-trans allethrin (O.3.3), d-trans allethrin (O.3.4), bifenthrin (O.3.5), bioallethrin (O.3.6), bioallethrin S-cylclopentenyl (O.3.7), bioresmethrin (O.3.8), cycloprothrin (O.3.9), cyfluthrin (O.3.10), beta-cyfluthrin (O.3.11), cyhalothrin (O.3.12), lambda-cyhalothrin (O.3.13), gamma-cyhalothrin (O.3.14), cypermethrin (O.3.15), alpha-cypermethrin (O.3.16), beta-cypermethrin (O.3.17), theta-cyperme
  • Nicotinic acetylcholine receptor agonists (nAChR): acetamiprid (O.4.1), clothianidin (O.4.2), cycloxaprid (O.4.3), dinotefuran (O.4.4), imidacloprid (O.4.5), nitenpyram (O.4.6), thiacloprid (O.4.7), thiamethoxam (O.4.8); (2E)-1-[(6-chloropyridin-3-yl)methyl]-N'-nitro-2-pentylidenehydra- zinecarboximidamide (O.4.9); 1-[(6-chloropyridin-3-yl)methyl]-7-methyl-8-nitro-5-propoxy- 1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridine (O.4.10); nicotine (O.4.11);
  • Nicotinic acetylcholine receptor allosteric activators spinosad (O.5.1), spinetoram (O.5.2); O.6 Chloride channel activators: abamectin (O.6.1), emamectin benzoate (O.6.2), ivermectin (O.6.3), lepimectin (O.6.4), milbemectin (O.6.5);
  • O.7 Juvenile hormone mimics hydroprene (O.7.1), kinoprene (O.7.2), methoprene (O.7.3); fenoxycarb (O.7.4), pyriproxyfen (O.7.5);
  • O.8 miscellaneous non-specific (multi-site) inhibitors methyl bromide (O.8.1) and other alkyl hal- ides; chloropicrin (O.8.2), sulfuryl fluoride (O.8.3), borax (O.8.4), tartar emetic (O.8.5);
  • O.10 Mite growth inhibitors clofentezine (O.10.1), hexythiazox (O.10.2), diflovidazin (O.10.3); etoxazole (O.10.4);
  • O.11 Microbial disruptors of insect midgut membranes the Bt crop proteins: Cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34/35Ab1;
  • O.12 Inhibitors of mitochondrial ATP synthase diafenthiuron (O.12.1); azocyclotin (O.12.2), cyhexatin (O.12.3), fenbutatin oxide (O.12.4), propargite (O.12.5), tetradifon (O.12.6);
  • Nicotinic acetylcholine receptor (nAChR) channel blockers bensultap (O.14.1), cartap hy- drochloride (O.14.2), thiocyclam (O.14.3), thiosultap sodium (O.14.4);
  • O.15 Inhibitors of the chitin biosynthesis type 0 bistrifluron (O.15.1), chlorfluazuron (O.15.2), diflubenzuron (O.15.3), flucycloxuron (O.15.4), flufenoxuron (O.15.5), hexaflumuron (O.15.6), lufenuron (O.15.7), novaluron (O.15.8), noviflumuron (O.15.9), teflubenzuron (O.15.10), tri- flumuron (O.15.11);
  • O.16 Inhibitors of the chitin biosynthesis type 1 buprofezin (O.16.1);
  • Ecdyson receptor agonists methoxyfenozide (O.18.1), tebufenozide (O.18.2), halofenozide (O.18.3), fufenozide (O.18.4), chromafenozide (O.18.5);
  • Octopamin receptor agonists amitraz (O.19.1);
  • Mitochondrial complex III electron transport inhibitors hydramethylnon (O.20.1), acequi- nocyl (O.20.2), fluacrypyrim (O.20.3);
  • Mitochondrial complex I electron transport inhibitors fenazaquin (O.21.1), fenpyroximate (O.21.2), pyrimidifen (O.21.3), pyridaben (O.21.4), tebufenpyrad (O.21.5), tolfenpyrad (O.21.6); rotenone (O.21.7);
  • O.23 Inhibitors of the of acetyl CoA carboxylase spirodiclofen (O.23.1), spiromesifen (O.23.2), spirotetramat (O.23.3);
  • O.24 Mitochondrial complex IV electron transport inhibitors aluminium phosphide (O.24.1), cal- cium phosphide (O.24.2), phosphine (O.24.3), zinc phosphide (O.24.4), cyanide (O.24.5);
  • O.26 Ryanodine receptor-modulators flubendiamide (O.26.1), chlorantraniliprole (O.26.2), cyan- traniliprole (O.26.3), cyclaniliprole (O.26.4), tetraniliprole (O.26.5); (R)-3-chloro-N1- ⁇ 2-methyl-4- [1,2,2,2 –tetrafluoro-1-(trifluoromethyl)ethyl]phenyl ⁇ -N2-(1-methyl-2-methyl- sulfonylethyl)phthalamide (O.26.6), (S)-3-chloro-N1- ⁇ 2-methyl-4-[1,2,2,2–tetrafluoro-1-(trifluoro- methyl)ethyl]phenyl ⁇ -N2-(1-methyl-2-methylsulfonylethyl)phthalamide (O.26.7), methyl-2-[3,5-di- bromo-2-(
  • O.27. insecticidal active compounds of unknown or uncertain mode of action afidopyropen (O.27.1), afoxolaner (O.27.2), azadirachtin (O.27.3), amidoflumet (O.27.4), benzoximate (O.27.5), bifenazate (O.27.6), broflanilide (O.27.7), bromopropylate (O.27.8), chinomethionat (O.27.9), cryolite (O.27.10), dicloromezotiaz (O.27.11), dicofol (O.27.12), flufenerim (O.27.13), flometoquin (O.27.14), fluensulfone (O.27.15), fluhexafon (O.27.16), fluopyram (O.27.17), flupyradifurone (O.27.18), fluralaner (O.27.19), me
  • component 2 The active substances referred to as component 2, their preparation and their activity e. g. against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commer- cially available.
  • the compounds described by IUPAC nomenclature, their preparation and their pesticidal activity are also known (cf. Can. J.
  • the present invention furthermore relates to agrochemical compositions comprising a mixture of at least one compound I (component 1) and at least one further active substance useful for plant protection, e. g. selected from the groups A) to O) (component 2), and if desired one suitable solvent or solid carrier. Furthermore, combating harmful fungi with a mixture of compounds of formula (I) and at least one fungicide from groups A) to O), as described above, is more efficient than combating those fungi with individual compounds (I) or individual fungicides from groups A) to O).
  • the order of application is not essential for working of the present invention.
  • the time between both applications may vary e. g. between 2 hours to 7 days. Also a broader range is possible ranging from 0.25 hour to 30 days, preferably from 0.5 hour to 14 days, particularly from 1 hour to 7 days or from 1.5 hours to 5 days, even more preferred from 2 hours to 1 day.
  • the weight ratio of the compo- nent 1) and the component 2) generally depends from the properties of the active components used, usually it is in the range of from 1:10,000 to 10,000:1, often it is in the range of from 1:100 to 100:1, regularly in the range of from 1:50 to 50:1, preferably in the range of from 1:20 to 20:1, more preferably in the range of from 1:10 to 10:1, even more preferably in the range of from 1:4 to 4:1 and in particular in the range of from 1:2 to 2:1.
  • the weight ratio of the component 1) and the component 2) usually is in the range of from 1000:1 to 1:1, often in the range of from 100: 1 to 1:1, regularly in the range of from 50:1 to 1:1, preferably in the range of from 20:1 to 1:1, more preferably in the range of from 10:1 to 1:1, even more preferably in the range of from 4:1 to 1:1 and in particular in the range of from 2:1 to 1:1.
  • the weight ratio of the component 1) and the component 2) usually is in the range of from 1:1 to 1:1000, often in the range of from 1:1 to 1:100, regularly in the range of from 1:1 to 1:50, preferably in the range of from 1:1 to 1:20, more preferably in the range of from 1:1 to 1:10, even more preferably in the range of from 1:1 to 1:4 and in particular in the range of from 1:1 to 1:2.
  • the weight ratio of component 1) and com- ponent 2) depends from the properties of the active substances used, usually it is in the range of from 1:100 to 100:1, regularly in the range of from 1:50 to 50:1, preferably in the range of from 1:20 to 20:1, more preferably in the range of from 1:10 to 10:1 and in particular in the range of from 1:4 to 4:1, and the weight ratio of component 1) and component 3) usually it is in the range of from 1:100 to 100:1, regularly in the range of from 1:50 to 50:1, preferably in the range of from 1:20 to 20:1, more preferably in the range of from 1:10 to 10:1 and in particular in the range of from 1:4 to 4:1.
  • any further active components are, if desired, added in a ratio of from 20:1 to 1:20 to the compo- nent 1).
  • compositions comprising as component 2) at least one active substance selected from: A) Respiration inhibitors
  • Inhibitors of complex III at Qo site e.g. strobilurins: azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3- methoxy-acrylic acid methyl ester and 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylidene- aminooxymethyl)-phenyl)-2-methoxyimino-N-methyl-acetamide, pyribencarb,triclopyricarb/chlo- rodincarb, f
  • inhibitors of complex II e. g. carboxamides: benodanil, bixafen, boscalid, carboxin, fen- furam,fluopyram, flutolanil, fluxapyroxad, furametpyr, isopyrazam, mepronil, oxycarboxin,pen- flufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, N-(4'-trifluoromethylthiobiphenyl-2-yl)- 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N-(2-(1, 3,3-trimethyl-butyl)-phenyl)-1, 3- dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, N-[9-(dichloromethylene)-1, 2, 3,4-tetrahydro-1, 4- methanonaphthalen-5-yl]-3-(difluoromethyl)-1-
  • respiration inhibitors e.g. complex I, uncouplers: diflumetorim, (5,8-difluoroquinazolin- 4-yl)-[2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl)-amine;
  • nitrophenyl derivates binapacryl, dinobuton, dinocap, fluazinam; ferimzone; organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide;
  • SBI fungicides Sterol biosynthesis inhibitors
  • DMI fungicides C14 demethylase inhibitors: triazoles: azaconazole, bitertanol,bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole,fenbuconazole, flu- quinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole,ipconazole, metconazole, my- clobutanil, oxpoconazole, paclobutrazole, penconazole,propiconazole, prothioconazole, sime- conazole, tebuconazole, tetraconazole, triadimefon,triadimenol, triticonazole, uniconazole; imid- azoles: imazalil, pefurazo
  • Delta14-reductase inhibitors aldimorph, dodemorph, dodemorph-acetate,fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine;
  • phenylamides or acyl amino acid fungicides benalaxyl, benalaxyl-M, kiralaxyl,metalaxyl, met- alaxyl-M (mefenoxam), ofurace, oxadixyl;
  • hymexazole octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, 5-fluoro-2-(p-tol- ylmethoxy) pyrimidin-4-amine, 5-fluoro-2-(4-fluorophenylmethoxy) pyrimidin-4-amine;
  • tubulin inhibitors such as benzimidazoles, thiophanates: benomyl, carbendazim,fuberidazole, thi- abendazole, thiophanate-methyl; triazolopyrimidines: 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2, 4, 6-trifluorophenyl)-[1, 2,4]triazolo[1, 5-a]pyrimidine
  • diethofencarb diethofencarb, ethaboxam, pencycuron, fluopicolide,zoxamide, met- rafenone, pyriofenone;
  • methionine synthesis inhibitors anilino-pyrimidines: cyprodinil, mepanipyrim,pyrimethanil;
  • blasticidin-S blasticidin-S, kasugamycin, kasugamycin hydrochloridehydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
  • MAP / histidine kinase inhibitors fluoroimid, iprodione, procymidone, vinclozolin,
  • G protein inhibitors quinoxyfen
  • Phospholipid biosynthesis inhibitors edifenphos, iprobenfos, pyrazophos,
  • inorganic active substances Bordeaux mixture, copper acetate, copper hydroxide,
  • copper oxychloride basic copper sulfate, sulfur;thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, metiram, propineb,thiram, zineb, ziram;organochlorine compounds (e.g.
  • inhibitors of glucan synthesis validamycin, polyoxin B; melanin synthesis inhibitors:pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil;
  • acibenzolar-S-methyl probenazole, isotianil, tiadinil, prohexadione-calcium
  • phosphonates fosetyl, fosetyl-aluminum, phosphorous acid and its salts
  • the present invention furthermore relates to mixtures comprising one compound of the formula I (component 1) and one pesticide II (component 2), wherein pesticide II is selected from the column "Co.2" of the B-1 to B-727 of Table B.
  • a further embodiment relates to the mixtures B-1 to B-727 listed in Table B, where a row of Table B corresponds in each case to a fungicidal mixture comprising as active components one the individualized compounds of formula (I), i.e.
  • compositions described in Table B comprise the active components in syn- ergistically effective amounts.
  • Table B Mixtures comprising as active components one indiviualized compound of the fomula I (in column Co. 1), and as component 2) (in column Co. 2) one pesticide from groups A) to O) [which is coded e. g. as (A.1.1) for azoxystrobin as defined above].
  • the mixtures of active substances can be prepared as compositions comprising besides the ac- tive ingredients at least one inert ingredient (auxiliary) by usual means, e. g. by the means given for the compositions of compounds of formula (I).
  • the mixtures of active substances according to the present invention are suitable as fungicides, as are the compounds of formula (I). They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, especially from the classes of the which de- rive especially from the following classes or are closely related to any of them: Solani, for example, but not limited to the genus Alternaria; fusarium or Rhizoctonia; Sorokiniana, for example, but not limited to the genus Bipolaris; Cinerea, for example, not limited to Botyris; Miyabeanus, not limited to Cochliobolus; Orbiculare, not limited to Colletotrichum; Teres, but not limited to Drechslera or Pyrenophora ; Repentis, but not limited to Tritici; Erysiphe spp.
  • Culmorum but not limited to Fusarium; Nivale, but not limited to Microdochium; Monilinia spp. e. g. M. laxa, M. fructicola and M. fructigena; Oryzae, but not limited to Bipolaris, Entyloma, Hemileia, Pyricularia and Rocladium; Pachyrhizi, but not limited to Phakopspora; Sclerotiorium, but not limited to Sclerotinia; Tritici, but not limited to Zymoseptoria; Basicola, but not limited to Thielaviopsis; Maydis, but not limited to Ustilago.
  • the mixtures of the active substances further show phytopathogenic activity against pathogens that are resistant to complex 2 or complex 3 respiratory chain inhibitors e.g: in Sclerotinia sclero- tiorum and/or Botyris cinerea.
  • phytopathogenic activity against pathogens that are resistant to complex 2 or complex 3 respiratory chain inhibitors e.g: in Sclerotinia sclero- tiorum and/or Botyris cinerea.
  • LCMS Liquid Chromatography Mass spectroscopy
  • Step 3a direct coupling of the 2 Trifluoromethyl thiophene 3 boronic acid
  • Dioxane water (60:200 ml) mixture was added to a round bottom flask containing compound 3 (70 mg). Added the boronic acid (50 mg) and K 2 CO 3 (71 mg) to the flask. Allowed it to degas for 15 min. Then added the Palladium catalyst (6 mg) to the reaction mixture. Allowed it to de- gas again for 5 min. Refluxed the reaction mixture at 110°C for 2 hrs. Reaction progress was monitored by TLC and LCMS. Once complete, the reaction mixture was filtered through celite. Washed thoroughly with ethyl acetate (EA). Extracted the crude compound with EA from aque- ous phase.
  • EA ethyl acetate
  • Na2SO4.Crude compound was purified by Yamazen by eluting with 20% ethylacetate : hexane mixture.5.72 g of the desired solid product 25 was obtained.
  • LCMS showed ⁇ 19% SM 1.
  • the reaction can also be carried out in DMF.
  • compound 6 KOH (3.0 eq) and the mixture was dissolved in DMF (10 vol). Stirred for 5 min and to this was added iodine granules (1.2 eq) portion wise at 25°C. Reaction mixture was stirred at same tem- perature for 4 hrs. Reaction was monitored by TLC. After completion of the reaction, ice water (100 ml) was added. A solid was precipitated. Stirred it for 15 min. Filtered it through Buchner funnel and washed with water and heptane. Solid was dried under vacuum at 50°C afforded 6.4 g of white solid compound.
  • Step 8 Acetic anhydride To a mixture of compound 19 (60 mg) in acetic anhydride (0.7 ml) was added TEA (0.052 g) and catalytic amount of DMAP (0.005 g). Resulting reaction mixture was stirred at 25°C for 1 h. Reaction was monitored by TLC. After completion of reaction, it was quenched with ice cold wa- ter (25 ml) and extracted with ethyl acetate (2 x 25 ml). Combined organic layer was washed with brine (25 ml). Organic layer was dried over Na 2 SO 4 and evaporated completely. Crude compound was purified by flash column chromatography. Pure compound was eluted with 10- 15% ethyl acetate : heptane solution. Evaporation of solvent afforded 0.035 g of the solid white compound 21.

Abstract

Heteroaryl compounds as agrochemical fungicides Formula (I) The present invention relates to heteroaryl compounds of formula (I) or a compound in the form of a stereoisomer, an agriculturally acceptable salt, a tautomer, an isotopic form, a N-oxide, a S- oxide, a prodrug or mixture thereof. The present invention further relates to the use of a com- pound of formula (I). Furthermore, the present invention relates to methods for combating phy- topathogenic harmful fungi, which methods comprising the steps of treatment of the phytopatho- genic fungi, the plant orthe plant propagation material selected from seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants to be protected against fungal attack, stored materials or harvest, or alternatelythe locus or soil or soil substituents or surfaces therefrom, with at least one compound of formula (I).

Description

Heteroaryl compounds as agrochemical fungicides Description
The present invention relates to heteroaryl compounds of formula (I) or a compound in the form of a stereoisomer, an agriculturally acceptable salt, a tautomer, an isotopic form, a N-oxide, a S-oxide, or a prodrug thereof; and the use of a compound of formula (I) and a compound of formula (II) or in the form of a stereoisomer, an agriculturally acceptable salt, a tautomer, an isotopic form, a N-oxide, a S-oxide, or a prodrug thereof, as an agrochemical fungicide. The in- vention further relates to agrochemical mixtures comprising at least one compound of formula (I); at least one further pesticidally active substance selected from the group consisting of herbicides, safeners, fungicides, insecticides, and plant growth regulators; and to agrochemical compositions comprising at least one such compound of the formula I and an auxiliary. Further encompassed by the present invention are methods for combating phytopathogenic harmful fungi, which meth- ods comprising the steps of treatment of the phytopathogenic fungi, the plant or the plant propa- gation material selected from seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants to be protected against fungal attack, stored materials or harvest, or alternately the locus or soil or soil substituents or surfaces there- from, with at least one compound of formula (I).
Fungal phyto pathogens infect many crops worldwide and therefore pose a serious threat to agriculture. The control of plant diseases and crop damage caused by fungal plant pathogens is extremely pertinent to achieve high crop yield and efficiency.
Natural products have garnered increasing focus in the discovery of agrochemicals as they can afford an opportunity to discover potential lead candidates with different biological activities and modes of action (Ming Zhi Zhang et al., Eur J. Med. Chem.53, 2012, 283-291).
Streptochlorin, an indole alkaloid produced by many species of marine actinomycetes, was first isolated as a new antibiotic in 1988 from the lipophilic extracts of the mycelium of a Strepto- myces species. Streptochlorin belongs to the class of naturally occurring 5-(3-indolyl) oxazoles, which also includes the natural product pimprinine. Streptochlorin has been claimed to have a variety of biological activities, such as antibiotic, antiallergic, antiangiogenic, anticancer, anti- tumor, antiproliferative, antityrosinase, antinematodal and pesticidal activity. Synthetic structural analogues of streptochlorin and pimprinine are known in the art to exhibit antifungal activity(Ming Zhi Zhang et al., Eur J. Med. Chem.92, 2015, 776-783).
US 2011207732 A1 discloses azaindole derivatives which are useful as medicaments. There is a continuous need for developing new fungicidal compounds which are effective in terms of activity spectrum, selectivity, sites of action, application rate, environmental safety and to retard or combat resistance development. In many cases, in particular at low application rates, the fungicidal activity of known fungicidal compounds is unsatisfactory
The inventors surprisingly found that the novel heteroaryl compounds of formula (I) have improved antifungal activity. The compounds are particularly effective as agrochemical fungicides and effective against a broad spectrum of phytopathogenic fungi. The compounds of formula (I) also effectively exhibit phytopathogenic fungal activity against pathogens which are resistant to complex 2 or complex 3 respiratory chain inhibitors. Accordingly, the present invention relates to the use of an heteroaryl compound of formula (I), wherein,
X denotes CR4 or N;
Figure imgf000003_0001
Y denotes CR5 or N;
A is selected from the group consisting of an unsubstituted or substituted 6-membered aryl; unsubstituted or substituted 5- or a 6-membered heterocycloalkyl; unsubstituted or substituted 5 or a 6-membered heterocycloalkenyl; and a unsubstituted or substi- tuted 5- or a 6-membered heteroaryl; wherein heterocycloalkyl, heterocycloalkenyl and heteroaryl contain besides carbon atoms, 1, 2, 3 or 4 heteroatoms independently selected from O, N or S as ring members; R1 is selected from the group consisting of hydrogen; -(CH2)aOR6; -(CH2)bC(=O)-R7; - C(=O)-(CH2)c-R8; -C(=O)-(CH2)d-OR9; -C(=O)-CR10(=CR11); -C(=O)-(CH2)e-SR12; - (CH2)f-O-C(=O)-R13; -(CH2)g-C(=O)-OR14; -C(=O)-O-(CH2)h-R15; -O-C(=O)-O-(CH2)i- R16; -C(=O)-NR17R18; -C(=S)-NR19R20; -NR21R22; -S(=O)j-R23; -(CH2)k-Si-(R24)l and - (CH2)m-O-(CH2)n-Si-(R25)0;
R2 is selected from the group consisting of hydrogen; halogen; CN; -C(=O)-OR14; unsub- stituted or substituted alkyl; unsubstituted or substituted cycloalkyl and unsubstituted or substituted cycloalkenyl;
R3 is selected from the group consisting of hydrogen, halogen; CN; -OR6, -C(=O)-OR14, unsubstituted or substituted alkyl; unsubstituted or substituted heteroalkyl; unsubsti- tuted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or sub- stituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substi- tuted heterocycloalkyl; and unsubstituted or substituted heterocycloalkenyl; R4 is selected from the group consisting of hydrogen and halogen;
R5 is selected from the group consisting of hydrogen; halogen; CN; unsubstituted or sub- stituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted al- kynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloal- kenyl; unsubstituted or substituted heterocycloalkyl and unsubstituted or substituted heterocycloalkenyl;
R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24 and R25 are independently of each other, selected from the group consisting of hydrogen; hal- ogen; CN; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; un- substituted or substituted alkynyl; unsubstituted or substituted cycloalkyl; unsubsti- tuted or substituted cycloalkenyl; unsubstituted or substituted aryl; unsubstituted or substituted -(alkylene)-aryl; unsubstituted or substituted heterocycloalkyl; unsubsti- tuted or substituted heterocycloalkenyl; unsubstituted or substituted heteroaryl; or
R17 together with R18 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
or
R19 together with R20 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
or
R21 together with R22 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
a is 0, 1, 2 or 3;
b is 0, 1, 2 or 3;
c is 0, 1, 2 or 3;
d is 0, 1, 2 or 3;
e is 0, 1, 2 or 3;
f is 0, 1, 2 or 3;
g is 0, 1, 2 or 3;
h is 1, 2 or 3;
i is 1, 2 or 3;
j is 0, 1, 2 or 3;
k is 0, 1, 2 or 3;
l is 0, 1, 2 or 3;
m is 0, 1, 2 or 3;
n is 0, 1, 2 or 3;
o is 1, 2 or 3;
or each of the compounds in the form of one or more stereoisomers, agriculturally accepta- ble salts, prodrugs, tautomers, isotopic forms, N-oxides, S-oxides or a mixture thereof, as an agricultural fungicide. In a further aspect, the present invention relates to a composition, comprising at least one compound of formula (I) as defined herein above or in the form of a stereoisomer or an agricul- turally acceptable salt or a tautomer or an isotopic form of a N-oxide or a S-oxide or a prodrug thereof, and an auxiliary.
In a further aspect, the present invention relates to an agrochemical mixture comprising at least one fertilizer; and at least one compound of formula (I) as defined herein above; or in the form of a stereoisomer or an agriculturally acceptable salt or a tautomer or an isotopic form or a N-oxide or a S-oxide or a prodrug thereof, and at least one pesticidally active substance selected from the group consisting of herbicides, safeners, fungicides, insecticides and plant growth regu- lators.
In another aspect, the present invention relates to a method for combating phytopathogenic harmful fungi, which process comprises treating the phytopathogenic fungi, the plant, or the plant propagation material selected from seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants to be protected against fungal attack, the stored materials or harvest, or alternately, the locus or soil or soil substituents or sur- faces therefrom, with an effective amount of at least one compound of formula (I) or an agricul- turally acceptable salt thereof or a tautomer or an isotopic form or a N-oxide or a S-oxide or a prodrug.
Although the present invention will be described with respect to particular embodiments, this description is not to be construed in a limiting sense.
Before describing in detail exemplary embodiments of the present invention, definitions im- portant for understanding the present invention are given. As used in this specification and in the appended claims, the singular forms of "a" and "an" also include the respective plurals unless the context clearly dictates otherwise. In the context of the present invention, the terms "about" and "approximately" denote an interval of accuracy that a person skilled in the art will understand to still ensure the technical effect of the feature in question. The term typically indicates a deviation from the indicated numerical value of ±20 %, preferably ±15 %, more preferably ±10 %, and even more preferably ±5 %. It is to be understood that the term "comprising" is not limiting. For the purposes of the present invention the term "consisting of" is considered to be a preferred embod- iment of the term "comprising of". If hereinafter a group is defined to comprise at least a certain number of embodiments, this is meant to also encompass a group which preferably consists of these embodiments only. Furthermore, the terms "first", "second", "third" or "(a)", "(b)", "(c)", "(d)" etc. and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be under- stood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein. In case the terms "first", "second", "third" or "(a)", "(b)", "(c)", "(d)", "i", "ii" etc. relate to steps of a method or use or assay there is no time or time interval coherence between the steps, i.e. the steps may be carried out simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between such steps, unless oth- erwise indicated in the application as set forth herein above or below. It is to be understood that this invention is not limited to the particular methodology, protocols, reagents etc. described herein as these may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention that will be limited only by the appended claims. Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art.
Unless otherwise indicated, the following definitions are set forth to illustrate and define the meaning and scope of the various terms used to describe the invention herein and the appended claims. These definitions should not be interpreted in the literal sense as they are not intended to be general definitions and are relevant only for this application.
It will be understood that‶substitution″,‶substituted″ or‶substituted with” means that one or more hydrogens of the specified moiety are replaced with a suitable substituent and includes the implicit proviso that such substitutions is in accordance with permitted valence of the substi- tuted atom and the substituent and results in a stable compound.
When any variable (for instance, R1, R2, R3, R4, R5 etc.) or substituent has more than one occurrence, its definition on each occurrence is independent at every other occurrence. Also com binations of substituents and/or variables are permissible only if such combinations result in stable compounds.
The term‶independently″ when used in the context of selection of substituents for a varia- ble, it means that where more than one substituent is selected from a number of possible substit- uents, those substituents may be the same or different.
Within the context of the present invention, the term‶alkyl″, as used herein, alone or as part of a substituent group refers to an acylic saturated aliphatic groups, including straight-chain or branched alkyl residues. Furthermore, the alkyl residue can be unsubstituted or substituted with one or more substituents, as in the case of C1-C6-alkyl, 1 to 6 carbon atoms. When one or more substituents deonote an alkyl residue or comprise an alkyl residue which is mono or polysubsti- tuted, this may be preferably be substituted with 1, 2, 3, 4 or 5 substituents independently selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -OH, -SH, -NH2, -NH(C1-C6)alkyl,-NH- CH(CH3)2, -N(C1-C6-alkyl)2, -N(C1-C6-alkyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, - C(=O)-O-C1-C6-alkyl, -C(=O)-O-phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -CH2-C(=O)-O- C1-C6-alkyl, -C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -NH-C(=O)C(CH3)3, -S(=O)- C1-C6-alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -NH-SO2-phenyl, - N(CH3)-SO2-phenyl, -C1-C6-alkyl, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2-C6H5, -Si-(C6H5)3, Si(C2H5)3, - Si-(CH3)2-C6H5, -Si-(C6H5)3, ethenyl, propenyl, isopropenyl, isobutenyl, isopentenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, furyl, oxazolyl, thiazolyl, pyra- zfirst olyl, thiophenyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; and wherein, the above stated alkyl, heterocycloalkyl, cycloalkyl, aryl or het- eroaryl are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, - SH, -O-CH3, -O-C2H5, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, oxo (=O), -O-phenyl and -O-2-pyridinyl. Particularly, preferred substitutents for alkyl may mutually inde- pendently be selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -CF3, -OH, -C(=O)CH3, -C(=O)-OH, -CH2-C(=O)-OH, -C(=O)OCH3, -C(=O)-O-phenyl, NH-C(=O)C(CH3)3, -Si-(CH3)3, - Si(C2H5)3, -Si-(CH3)2-C6H5, -Si-(C6H5)3, phenyl and -CH2-phenyl.
Representative examples of alkyl which may be unsubstituted or mono- or polysubstituted include, but not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexytl, isopropyl, isobutyl, tertiary butyl, isopentyl, 2-methylbutyl, 3-methylbutyl and the like. Polysubstituted alkyl residues are understood to be those alkyl residues which are polysubstituted, preferably di- or trisubsti- tuted, either on different or on the same carbon atoms, for example trisubstituted on the same C atom as in the case of -CF3 or at different locations as the case of–(CHCl)-(CH2)F. Polysubstitu- tion may proceed with identical or different substituents. Representative examples of suitable substituted alkyl residues which may include, but not limited to, -CF3, -CF2H, -CFH2, -CH2Cl, - (CH2)-OH, -(CH2)-(CF3), -(CH2)-(CH2)-NH2, -(CH2)-C(=O)-OH, -CH(CH3)2-OH -CH(CF3)-OH, - (CH2)-(CH2)-C(=O)-OH, -(CH2)-C(=O)-OCH3, -(CH2)-N(CH3)2, -(CF2)-(CF3), -(CH2)-(CH2)-(CH2)- (CH2)-Cl and -(CH2)-(CH2)-NH-C(=O)-O-C(CH3)3.
Within the context of the present invention, the term‶alkenyl″, as used herein, refers to acyclic unsaturated hydrocarbon residues, including straight-chain or branched alkenyl residues, and comprise at least one double bond, preferably 1, 2, or 3 double bonds, with as in the case of C2 C6 alkenyl, 2 to 6 C atoms. Furthermore, the alkenyl residue can be unsubstituted or substi tuted with one or more substituents, as in the case of C2-C6-alkenyl, 2 to 6 carbon atoms. When one or more substituents denote an alkenyl residue or comprise an alkenyl residue which is mono or polysubstituted, this may be optionally be substituted with 1, 2, 3, 4 or 5 substituents or prefer- ably be substituted with 1, 2 or 3, substituents independently selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -CCl3, -CF3, -OH, -SH, -NH2, -NH(C1-C6)alkyl,-NH-CH(CH3)2, -N(C1-C6- alkyl)2, -N(C1-C6-alkyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, - C(=O)-O-phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -CH2-C(=O)-O-C1-C6-alkyl, -C(=O)- NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -NH-C(=O)C(CH3)3, -S(=O)-C1-C6-alkyl, -S(=O)- phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -NH-SO2-phenyl, -N(CH3)-SO2-phenyl; -C1-C6-alkyl, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2-C6H5, -Si-(C6H5)3, -O(CH2)2-Si(CH3)3, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tertiary butyl, pentyl, hexyl, heptanyl, ethenyl, propenyl, isopro- penyl, isobutenyl, isopentenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopentyl, cy- clohexyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrim- idinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; and wherein, the above stated alkyl, heter- ocycloalkyl, cycloalkyl, aryl or heteroaryl are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, oxo (=O), -O-phenyl and -O-2-pyridinyl.
Particularly, preferred substitutents for alkyl may mutually independently be selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -CCl3, -CF3, -OH, -C(=O)CH3, -C(=O)-OH, -CH2- C(=O)-OH, -C(=O)OCH3, -C(=O)-O-phenyl, NH-C(=O)C(CH3)3, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2- C6H5, -Si-(C6H5)3, -O(CH2)2-Si(CH3)3, ethenyl, propenyl, ethynyl, furyl, oxazolyl, thiazolyl, pyra- zolyl, thiophenyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl, and -CH2-phenyl. Examples of substituted alkyl include but not limited to methyl, ethyl, hy- droxymethyl, 2-chlorobutyl, fluoromethyl, 1,1-difluoromethyl, trifluoromethyl, trichloromethyl, 1,1,1,2,2-pentafluoroethyl, 1,1,2,2– tetrafluoroethyl or aminomethyl.
Representative examples for alkenyl which may be unsubstituted or mono- or polysubsti- tuted include, but not limited to, ethenyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 4-pentenyl, hexenyl, -CH=C(CH3)2 and the like. Polysubstituted alkyl residues are understood to be those alkenyl residues which are polysubstituted, preferably disubstituted, either on different or on the same carbon atoms, for example disubstituted on the same C atom as in the case of - CH=CCl2, or at different locations as in the case of–CCl=CH-(CH2)-NH2. Polysubstitution may proceed with identical or different substituents.
Within the context of the present invention, the term‶alkynyl″, as used herein, refers to acyclic unsaturated hydrocarbon residues, including straight-chain or branched alkenyl residues, and comprise at least one triple bond, preferably 1 or 2 triple bonds, with as in the case of C2-C6 alkynyl, 2 to 6 C atoms. Furthermore, the alkynyl residue can be unsubstituted or substituted with one or more substituents, as in the case of C2-C6-alkynyl, 2 to 6 Carbon atoms. When one or more substituents denote an alkenyl residue or comprise an alkenyl residue which is mono or polysub- stituted, this may be optionally be substituted with 1, 2, 3, 4 or 5 substituents or preferably be substituted with 1, 2 or 3, substituents independently selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -OH, -SH, -NH2, -NH(C1-C6)alkyl,-NH-CH(CH3)2, -N(C1-C6-alkyl)2, -N(C1-C6-alkyl)- phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phenyl, -CH2- C( O) OH, CH2 C( O) C1 C6 alkyl, CH2 C( O) O C1 C6 alkyl, C( O) NH2, C( O) NH(C1 C6)alkyl, -C(=O)-NH-phenyl, -NH-C(=O)C(CH3)3, -S(=O)-C1-C6-alkyl, -S(=O)-phenyl, -S(=O)2-C1- C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -NH-SO2-phenyl, -N(CH3)-SO2-phenyl, -C1-
Figure imgf000008_0001
(CH3)3, -Si(C2H5)3, -Si-(CH3)2-C6H5, -Si-(C6H5)3, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tertiary butyl, pentyl, hexyl, heptanyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, furyl, oxa- zolyl, thiazolyl, pyrazolyl, thiophenyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; wherein, the above stated alkyl, heterocycloalkyl, cycloalkyl, aryl or heteroaryl are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, - NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, oxo (=O), -O-phenyl and -O-2-pyridinyl.
Particularly, preferred substitutents for alkynyl may mutually independently be selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -CF3, -OH, -C(=O)CH3, -C(=O)-OH, -CH2-C(=O)- OH, -C(=O)OCH3, -C(=O)-O-phenyl, NH-C(=O)C(CH3)3, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2-C6H5, - Si-(C6H5)3, phenyl, and -CH2-phenyl.
Representative examples for alkynyl which may be unsubstituted or mono- or polysubsti- tuted include, but not limited to, ethynyl, 1-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, hexynyl and the like. Polysubstituted alkynyl residues are un- derstood to be those alkynyl residues which are polysubstituted, preferably disubstituted, either on different or on the same carbon atoms. Representative examples of alkynyl residues include, but not limited to, -C≡C-Si(CH3)3, -C≡C-Si(CH2)2-CH3 and -C≡C-Si(CH2)2-C6H5.
Within the context of the present invention, the term‶heteroalkyl″, as used herein, denotes an alkyl residue described hereinabove, in which one or more C atoms have been replaced by a heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur. Heteroalkyl resi- dues may preferably comprise 1, 2, 3, 4, 5 or 6 carbon atoms and 1, 2 or 3 heteroatom(s) inde- pendently of each other selected from the group consisting of oxygen, nitrogen and sulfur. Par- ticularly preferred heteroalkyl residues may be 2 to 6-membered.
Representative examples of suitable heteroalkyl residues which may in each case by un- substituted or mono- or polysubstituted, are -O-CH3, -O-CH2-CH3, -CH2-O-CH3, -CH2-O-C2H5, - CH2-O-CH(CH3)2, -CH2-O-CH3, -CH2-S-CH3, -CH2-NH-CH3, -CH2-NH-C2H5, -CH2-NH-CH(CH3)2, - CH2-NH-CH3, -CH2-NH-(CH3)3, -CH2-CH2-O-CH3, -CH2-CH2-O-C2H5, -CH2-CH2-O-CH(CH3)2, - CH2-CH2-O-(CH3)3, -CH2-CH2-S-CH3, -CH2-CH2-S-C2H5, -CH2-CH2-S-CH(CH3)2, -CH2-CH2-S- (CH3)3, -CH2-S-CH2-O-CH3, -CH2-CH2-NH-CH3, -CH2-CH2-NH-C2H5, -CH2-CH2-NH-CH(CH3)2, - CH2-CH2-NH-(CH3)3, -CH2-O-CH2-O-C2H5, -CH2-O-CH2-O-C2H5, -CH2-O-CH2-O-CH(CH3)2, -CH2- O-CH2-O-(CH3)3, CH2-S-CH2-O-(CH3)3 and -CH2-NH-CH2-S-(CH3)3.
Within the context of the present invention, the term‶heteroalkenyl″, as used herein, refers to an alkenyl residue described hereinabove, in which one or more C atoms have been replaced by a heteroatom independently selected from the group consisting of oxygen, nitrogen and sulfur. Heteroalkenyl residues may preferably comprise 1, 2, 3, 4, 5 or 6 carbon atoms and 1, 2 or 3 heteroatom(s) independently of each other selected from the group consisting of oxygen, nitrogen and sulfur as chain links and may preferably be 2- to 6-membered. Representative examples of suitable heteroalkenyl residues may include, but not limited to, -CH2-O-CH=CH-(CH2)-OH; -CH2- S-CH=CH-(CH2)-NH2; and -CH2-NH-CH=CH-CN. Within the context of the present invention, the term heteroalkynyl , as used herein, refers to an alkenyl residue described hereinabove, in which one or more C atoms have been replaced by a heteroatom independently of each other selected from the group consisting of oxygen, nitro- gen and sulfur. Heteroalkenyl residues may preferably comprise 1, 2, 3, 4, 5 or 6 carbon atoms and 1, 2 or 3 heteroatom(s) independently selected from the group consisting of oxygen, nitrogen and sulfur as chain links and may preferably be 2- to 6-membered. Representative examples of suitable heteroalkynyl residues may include, but not limited to, -CH2-O-C≡CH, -CH2-S-C≡CH, - CH2-CH2-O-C≡CH and–CH2-CH2-S-C≡CH.
Within the context of the present invention and as used herein, the term“cycloalkyl” refers to a saturated cyclic hydrocarbon residue including preferably 3, 4, 5, 6, 7, 8, 9 or 10 C atoms, as ring members; and more preferably refers to a cycloalkyl with 3, 4, 5, 6 or 7 carbon atoms. The cycloalkyl group may be unsubstituted or monosubstituted or identically or differently polysubsti- tuted. Representative examples of cycloalkyl include, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.
Within the context of the present invention and as used herein, the term‶cycloalkyl″refers to a cyclic unsaturated hydrocarbon residue including preferably 3, 4, 5, 6, 7, 8, 9 or 10 C atoms, as ring members; and more preferably refers to a cycloalkyl with 3, 4, 5, 6 or 7 carbon atoms. The cycloalkenyl group may be unsubstituted or monosubstituted or identically or differently pol- ysubstituted. Representative examples of cycloalkenyl include, but not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl cyclohexadienyl, cycloheptenyl and cycloheptadienyl.
Within the context of the present invention and as used herein, the term‶heterocycloalkyl″ refers to a cyclic saturated hydrocarbon residue with preferably 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, preferably with 3, 4, 5, 6 or 7 carbon atoms, wherein, one or more C atoms are replaced heteroatoms independently selected from oxygen, nitrogen and sulfur. Heterocycloalkyl residues may preferably comprise 1, 2, or 3 heteroatom(s) mutually independently selected from the group consisting of oxygen, sulfur and nitrogen as ring members. A heterocycloalkyl residue may be unsubstituted or monosubstituted or identically or differently polysubstituted. Heterocycloalkyl res- idues may preferably be 3 to 7 membered and more preferably 5 to 7-membered.
Representative examples of heterocycloalkyls include, but not limited to, tetrahydrofuranyl, tetrahydrothiophenyl, tetrahydropyranyl, oxetanyl, piperidinyl, piperazinyl, morpholinyl, thiomor- pholinyl, 1,2,4-oxadiazonyl, 1,2,4-thiodiazonyl, 1,3,4-trimethyl piperazinyl, 2-piperidinyl, 3-piperi- dinyl, 4-piperidinyl, 1,3-dioxan-5-yl, tetrahydropyrimidinyl, tetrahydropyrazinyl and tetrahydro- pyridazinyl.
Within the context of the present invention and as used herein, the term‶heterocycloalkenyl ″ refers to a cyclic unsaturated hydrocarbon residue with preferably 4, 5, 6, 7, 8, 9 or 10 carbon atoms, preferably with 4, 5, 6 or 7 carbon atoms, which comprises at least one double bond, and wherein, one or more C atoms are replaced by heteroatoms independently selected from oxygen, nitrogen and sulfur. Heterocycloalkenyl residues may preferably comprise 1, 2, or 3 heteroatom(s) mutually independently selected from the group consisting of oxygen, sulfur and nitrogen as ring members. A heterocycloalkenyl residue may be unsubstituted or monosubstituted or identically or differently polysubstituted. Heterocycloalkenyl residues may preferably be 4 to 9 membered and more preferably 5 to 7-membered.
Representative examples of heterocycloalkenyls include, but not limited to, (2,3)-dihydro- furanyl, (2,3)-dihydrothienyl, (2,3)-dihydropyrrolyl, (2,5)-dihydropyrrolyl, (2,5)-dihydropyrrolyl, (2,3) dihydroisoxazolyl, (1,4) dihydropyridin 1 yl, dihydropyranyl, 2,3 dihydropyrazol 1 yl, 2,3 di hydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4- dihydropyrazol-1-yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 4,5-dihydropyrazol-2-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,5-dihydrothienyl and (1,2,3,4)-tetrahydropyridin-1-yl.
The cycloalkyl, heterocycloalkyl, cycloalkenyl or heterocycloalkenyl residues may be fused with an unsubstituted or at least monosubstituted mono- or bicyclic ring system. Within the context of the present invention, a mono- or bicyclic ring system should be understood to mean mono- or bicyclic hydrocarbon residues which may be saturated, unsaturated or aromatic and optionally comprise one or more heteroatoms as ring members. The above-stated mono- or bicyclic ring systems are 4-, 5- or 6-membered and may in each case preferably optionally comprise 0, 1, 2, 3, 4, or 5 heteroatoms, specifically, optionally 0, 1 or 2 heteroatoms as ring members, inde- pendently selected from the group consisting of oxygen, nitrogen and sulfur. In bicyclic ring sys- tems, the different rings may, in each case may indepedendently exhibit a different degree of saturation, i.e. be saturated, unsaturated or aromatic.
When one or more substituents comprise a monocyclic or bicyclic ring system, which is mono- or polysubstituted, this may be optionally substituted with 1, 2, or 3 substituents, which may be independently selected from the group consisting of F, Cl , Br, I, -CN, -NH(C1-C6)alkyl, - NH-CH(CH3)2, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phe- nyl, -C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, -NH-C(=O)C(CH3)3, -S(=O)2-C1-C6-alkyl, -S(=O)2-phe- nyl, -S(=O)2-NH2, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, ethenyl, ethynyl, propynyl, -CF3, oxo (=O), cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazi- nyl, phenyl and -CH2-phenyl; wherein, the cycloalkyl, heterocyloalkyl, aryl and heteroaryl are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -NH2, -CF3, -OH, -SH, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tertiary butyl, -OCH3, -O-phenyl, -O-CH2-phenyl, -OCF3 and -C(=O)-O-CH3.
Unless stated otherwise, when one or more substituents denote a cycloalkyl, heterocyclo- alkyl, cycloalkenyl or heterocycloalkenyl which are mono substituted or polysubstituted, this may be optionally substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -C(=O)-H, - C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phenyl, -C(=O)-NH2, -C(=O)- NH(C1-C6)alkyl, -NH-C(=O)C(CH3)3, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -C1-C6-al- kyl, -CF3, oxo (=O), cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, furyl, oxazolyl, thiazolyl, py- razolyl, thiophenyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; wherein, the alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl, are them- selves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -NH2, -CF3, -OH, -SH, methyl, ethyl, n- propyl, n-butyl, isopropyl, isobutyl, tertiary butyl, -OCH3, -O-phenyl, -O-CH2-phenyl, -OCF3 and - C(=O)-O-CH3. Particularly preferred substituents, may independently be selected from the group consisting of F, Cl, Br, I, CN, C1 C6 alkyl, CF3, oxo ( O), cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl and -CH2-phenyl; wherein, the said alkyl, cycloalkyl or aryl are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -NH2, -CF3, -OH, -SH, methyl, ethyl, n-propyl, n- butyl, isopropyl, isobutyl, tertiary butyl, -OCH3, -O-phenyl, -O-CH2-phenyl, -OCF3 and -C(=O)-O- CH3.
Within the context of the present invention and as used herein, the term‶aryl″, refers to a monocyclic, bicyclic or tricyclic hydrocarbon ring system having 6, 10 or up to 14 ring carbon atoms, wherein at least one carbocyclic ring is having a ^-electron system. An aryl residue may be unsubstituted, monosubstituted or identically or differently polysubstituted. Examples of phenyl residues include, phenyl, 1-naphthyl, 2-naphthyl or anthracenyl.
Within the context of the present invention and as used herein, the term‶heteroaryl″ refers to an aromatic monocyclic, bicyclic or a tricyclic hydrocarbon containing 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms, particularly, preferably with 5, 6, 9 or 10 atoms and more particularly, with 5 or 6 carbon atoms, in which one to four carbon atoms are replaced by identical or different hetero atoms selected from the group consisting of oxygen, sulfur and nitrogen. Heteroaryl resi- dues may preferably comprise 1, 2, 3, 4 or 5, particularly preferably 1, 2, or 3, heteroatoms inde- pendently selected from the group consisting of oxygen, sulfur and nitrogen. A heteroaryl residue may be unsubstituted or monosubstituted or identically or differently polysubstituted.
Representative examples of suitable heteroaryl residues include, but not limited to, furyl, pyridyl, oxazolyl, thiazolyl, pyrazolyl, pyrimidinyl, pyrrolyl, isooxazolyl, triazolyl, tetrazolyl, pyridazi- nyl, isothiazolyl, benzothiazolyl, benzooxazolyl, benzimidazolyl, quinolinyl or isoquinolinyl.
The aryl or heteroaryl residues may be fused with a mono- or bicyclic ring system defined as above. Representative examples of aryl rings fused with a mono or bicyclic ring system include, but not limited to, 2,3-dihydrobenzo[b]thiophenyl, 2,3-dihydro-1H-indenyl, indolinyl, 2,3-dihydro- benzofuranyl, 2,3-dihydrobenzo[d]oxazolyl, benzo[d][1,3]dioxolanyl, isoindolinyl, 1,2,3,4- tetrahy- dronaphthyl, 1,2,3,4 tetrahydroquinolinyl, 1,2,3,4-tetrahydroisoquinolinyl, chromanyl, thiochroma- nyl, 3,4-dihydro-2H-benzo[1,4]oxazinyl and 3,4-dihydro-2H-benzo[1,4]thiazinyl.
Unless stated otherwise, when one or more substituents denote an aryl or heteroaryl resi- due or comprise an aryl or heteroaryl residue, which are mono substituted or polysubstituted, this may be optionally substituted with 1, 2, 3, 4 or 5 substituents independently selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -OH, -SH, -O-CH3, -O-C2H5 -NH2, -NH(C1-C6)alkyl, - NH-CH(CH3)2, -N(C1-C6-alkyl)2, -N(C1-C6-alkyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)- OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -C(=O)- NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -S(=O)-C1-C6-alkyl, -S(=O)-phenyl, -S(=O)2-C1- C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -NH-SO2-phenyl, -N(CH3)-SO2-phenyl, -C1-C6
Figure imgf000011_0001
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl, -CH2-phenyl, -O- phenyl, -O-CH2-phenyl and O-2-pyridinyl; wherein the alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, - O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, - O-phenyl and -O-2-pyridinyl. Particularly preferred substituents, may be independently selected from the group consist ing of F, Cl, Br, I, -NO2, -CN, -OH, -SH, -O-CH3, -O-C2H5, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, - C(=O)-O-phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -S(=O)-C1-C6-alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, C1- C6-alkyl, -CF3, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl, -CH2- phenyl, -O-phenyl and -O-CH2-phenyl; wherein the alkyl, cycloalkyl, heterocycloalkyl, aryl or het- eroaryl are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, - SH, -O-CH3, -O-C2H5, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, -O-phenyl and -O-2-pyridinyl.
Aryl radicals may be substituted in any desired position. For example, in monosubstituted phenyl, the substitutent may be located in the 2-position, the 3-position, the 4-position or the 5- position. If the phenyl carries two substituents, they can be located in 2, 3-position, 2, 4- position, 2, 5-position, 2, 6-position, 3, 4-position or 3, 5-position. Representative examples of monosub- stituted and polysubstituted phenyl groups include, but not limited to, 2-fluorophenyl, 3-fluoro- phenyl, 4-fluorophenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2-aminophenyl, 3- aminophenyl, 4-aminophenyl, 2-dimethylaminophenyl, 2-dimethylaminophenyl, 3-dimethyla- minophenyl, 4-dimethylaminophenyl, 2-methylsulfinyl phenyl, 3-methylsulfinyl phenyl, 4-methyl- sulfinyl phenyl, 2-methylsulfonyl phenyl, 3-methylsulfonyl phenyl, 4-methylsulfonyl phenyl, 2- methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-carboxy phenyl, 3-carboxyphenyl, 4-car- boxyphenyl, 2-ethylphenyl, 3-ethyl phenyl, 2-trifluoromethyl phenyl, 3-trifluorophenyl, 4-trifluoro- phenyl and 5-trifluoromethyl-2-pyridyloxy-benzene, 3, 5-difluorophenyl, 2,6-difluorophenyl, 2-me- thyl-3-fluorophenyl, 5-fluoro-6-methylphenyl, 2-methoxy-3-fluorophenyl and 3-chloro-5-trifluoro- methyl-2-pyridyloxy-benzene.
The term‶heteroatom″ as used herein, includes nitrogen (N), oxygen (O) and sulfur (S). Any heteroatom with unsatisfied valency is assumed to have a hydrogen atom or a C1-C6-alkyl group to satisfy the valency.
Within the context of the present invention and as used herein, interchangeably throughout this application, the terms‶compounds of formula (I)″,‶compounds of formula I(A)″;‶compounds of formula I(B)″;‶compounds of formula I(C)″;‶compounds of formula I(D)″;‶compounds of for- mula I(E)″;‶compounds of formula I(F)″;‶compounds of formula I(G)″;‶compounds of formula I(H)″;‶compounds of formula I(I)″;‶compounds of formula I(J)″;‶compounds of formula I(K)″;‶ compounds of formula I(L)″;‶compounds of formula I(M)″;‶compounds of formula I(N)″;‶com- pounds of formula I(O)″;‶compounds of formula I(P)″;‶compounds of formula I(Q)″;‶compounds of formula I(R)″;‶compounds of formula I(S)″;‶compounds of formula I(T)″;‶compounds of for- mula I(U)″; (described in embodiments below)″, and“compounds of the present invention" include all the stereoisomeric and tautomeric forms and mixtures thereof in all ratios, prodrugs, isotopic forms, their agriculturally acceptable salts, N-oxides and S-oxides thereof.
Within the context of the present invention and as used herein, the term "stereoisomer" is a general term used for all isomers of individual compounds that differ only in the orientation of their atoms in space. The term stereoisomer includes mirror image isomers (enantiomers), mixtures of mirror image isomers (racemates, racemic mixtures), geometric (cis/trans or E/Z) isomers, and isomers of compounds with more than one chiral center that are not mirror images of one another (diastereoisomers).
Within the context of the present invention and as used herein, the term“tautomer” refers to the coexistence of two (or more) compounds that differ from each other only in the position of one (or more) mobile atoms and in electron distribution, for example, keto-enol tautomers.
The term "agriculturally acceptable salts" as used herein, includes salts of the active com- pounds which are prepared with acids or bases, depending on the particular substituents found on the compounds described herein.
Within the context of this present application and as used herein, the term“isotopic forms” or“isotopically labeled forms” is a general term used for isotopic forms of compounds of formula, wherein one or more atoms of compounds of formula (I); I(A); I(B); I(C); I(D); I(E); I(F); I(G); I(H); I(I); I(J); I(K); I(L); I(M); I(N); I(O); I(P); I(Q); I(R); I(S); I(T); I(U), are replaced by their respective isotopes. All isotopes of any particular atom or element as specified are contemplated within the scope of the compounds of the invention. Examples of isotopes that may be incorporated into the compounds disclosed herein include, but are not limited to, isotopes of hydrogen such as 2H (deuterium or D) and 3H, carbon such as 11C, 13C and 14C, nitrogen such as 13N and 15N, oxygen such as 15O, 17O and 18O, chlorine such as 36Cl, fluorine such as 18F and sulphur such as 35S.
Representative examples of isotopic forms of the compounds of formula (I) may include, without limitation, deuterated compounds of formula I(A); I(B); I(C); I(D); I(E); I(F); I(G); I(H); I(I); I(J); I(K); I(L); I(M); I(N); I(O); I(P); I(Q); I(R); I(S); I(T); I(U). The term "deuterated" as used herein, by itself or used to modify a compound or group, refers to replacement of one or more hydrogen atom(s), which is attached to carbon(s), with a deuterium atom. For example, the compounds of formula (I) or I(A) or I(B) or I(C) or I(D) or I(E) or I(F) or I(G) or I(H) or I(I) or I(J) or I(K) or I(L) or I(M) or I(N) or I(O) or I(P) or I(Q) or I(R) or I(S) or I(T) or I(U) or may include in the definitions of one or more of the various variables, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37, R38, R39, R40, R41, R42, R43, R44, R45, R46, R47, R48, R49, R50, R51,
Figure imgf000013_0001
R53, R54, R55, R56, R57, R58, R59, R60, R61, R62, R63, R64, R65, R66, R67, R68, R69, R70, R71, R72, R73, R74, R75, R76, R77, R78, R79, R80, R81, R82, R83, R84, R85, R86, R87, R88, R89, R90, R91, R93, R95, R96, R97, R98, R99, R100, R101, R102, R103, R104, R105, R106, R107, R108, R109, R110, R111, R112, R113, R114, R115 or R116, wherever applicable, deuterium, deuterated-alkyl, deuterated-heterocycloalkyl, deuterated-aryl, deuter- ated-heteroaryl and the like.
Within the context of the present invention and as used herein,“N-oxide” refers to the oxide of the nitrogen atom of a nitrogen-containing heteroaryl or heterocycle. N-oxide can be formed in the presence of an oxidizing agent for example peroxide such as m-chloro-perbenzoic acid or hydrogen peroxide. N-oxide refers to an amine oxide, also known as amine-N-oxide, and is a chemical compound that contains N ^O bond.
Within the context of the present invention and as used herein,“S-oxide” refers to the oxide of the sulfur atom (S-oxide) or dioxide of the sulfur atom (S,S-dioxide) of a sulfur-containing het- eroaryl or heterocycle. S-oxide and S,S-dioxides can be in the presence of an oxidizing agent for example peroxide such as m-chloro-perbenzoic acid or oxone.
Within the context of the present invention and as used herein, the term“prodrug” as used herein refers to compounds of formula (I), that are compound precursors, which following appli- cation, release the active ingredient or the parent compound via a chemical or metabolic process, for example, a prodrug on being brought to the physiological pH or through an enzyme action is converted to the desired active ingredient having the fungicidal effect. The compounds of formula (I) are prodrugs, wherein R1 is selected from the group consisting of -(CH2)aOR6; -(CH2)bC(=O)- R7; -C(=O)-(CH2)c-R8; -C(=O)-(CH2)d-OR9; -C(=O)-CR10(=CR11); -C(=O)-(CH2)e-SR12; -(CH2)f-O- (C=O)-R13; -(CH2)g-C(=O)-OR14; -C(=O)-O-(CH2)h-R15; -O-C(=O)-O-(CH2)i-R16; -C(=O)-NR17R18; - C(=S)-NR19R20; -NR21R22; -S(=O)j-R23; -(CH2)k-Si-(R24)l and -(CH2)m-O-(CH2)n-Si-(R25)0; wherein, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24 and R25 are as defined hereinabove.
Within the context of the present invention and as used herein, the term“bio-cleavable amino protecting group” is intended to refer to a group that can be selectively attached to the nitrogen atom by chemical modification of an amino group so as to selectively inhibit participation of the amino group in chemical reactions. However, these amino protecting groups can be cleaved either chemically or enzymatically. Exemplary bio-cleavable amino-protecting groups include car- bamates (urethanes) selected from methyl, ethyl and tertiary butyl (i.e. BOC or tert-butoxy car- bonyl) and amides selected from acetyl and methoxyacetyl. The procedures for the formation of the above mentioned bio-cleavable amino protecting groups are based on the known methods and their relevant references as cited in T. W. Greene, Protective Groups in Organic Synthesis”, Third Edition, 1999, John Wiley and Sons, New York, are incorporated herein as a reference.
In a first embodiment, the present invention relates to the use of an heteroaryl compound of formula (I),
Figure imgf000014_0001
formula (I)
wherein,
X denotes CR4 or N;
Y denotes CR5 or N;
A is selected from the group consisting of an unsubstituted or substituted 6-membered aryl; unsubstituted or substituted 5- or a 6-membered heterocycloalkyl; unsubstituted or substituted 5 or a 6-membered heterocycloalkenyl; and a unsubstituted or substi- tuted 5- or a 6-membered heteroaryl; wherein heterocycloalkyl, heterocycloalkenyl and heteroaryl contain besides carbon atoms, 1, 2, 3 or 4 heteroatoms independently selected from O, N or S as ring members; R1 is selected from the group consisting of hydrogen; -(CH2)aOR6; -(CH2)bC(=O)-R7; - C(=O)-(CH2)c-R8; -C(=O)-(CH2)d-OR9; -C(=O)-CR10(=CR11); -C(=O)-(CH2)e-SR12; - (CH2)f-O-C(=O)-R13; -(CH2)g-C(=O)-OR14; -C(=O)-O-(CH2)h-R15; -O-C(=O)-O-(CH2)i- R16; -C(=O)-NR17R18; -C(=S)-NR19R20; -NR21R22; -S(=O)j-R23; -(CH2)k-Si-(R24)l and - (CH2)m-O-(CH2)n-Si-(R25)0; R is selected from the group consisting of hydrogen; halogen; CN; C( O) OR ; unsub stituted or substituted alkyl; unsubstituted or substituted cycloalkyl and unsubstituted or substituted cycloalkenyl;
R3 is selected from the group consisting of hydrogen, halogen; CN; -OR6, -C(=O)-OR14, unsubstituted or substituted alkyl; unsubstituted or substituted heteroalkyl; unsubsti- tuted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or sub- stituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substi- tuted heterocycloalkyl; and unsubstituted or substituted heterocycloalkenyl;
R4 is selected from the group consisting of hydrogen and halogen;
R5 is selected from the group consisting of hydrogen; halogen; CN; unsubstituted or sub- stituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted al- kynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloal- kenyl; unsubstituted or substituted heterocycloalkyl and unsubstituted or substituted heterocycloalkenyl;
R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24 and R25 are independently of each other, selected from the group consisting of hydrogen; hal- ogen; CN; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; un- substituted or substituted alkynyl; unsubstituted or substituted cycloalkyl; unsubsti- tuted or substituted cycloalkenyl; unsubstituted or substituted aryl; unsubstituted or substituted -(alkylene)-aryl; unsubstituted or substituted heterocycloalkyl; unsubsti- tuted or substituted heterocycloalkenyl; unsubstituted or substituted heteroaryl; or
R17 together with R18 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
or
R19 together with R20 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substituted; or
R21 together with R22 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substituted;
a is 0, 1, 2 or 3;
b is 0, 1, 2 or 3;
c is 0, 1, 2 or 3;
d is 0, 1, 2 or 3;
e is 0, 1, 2 or 3;
f is 0, 1, 2 or 3;
g is 0, 1, 2 or 3;
h is 1, 2 or 3;
i is 1, 2 or 3;
j is 0, 1, 2 or 3;
k is 0, 1, 2 or 3;
l is 0, 1, 2 or 3; m is 0, 1, 2 or 3;
n is 0, 1, 2 or 3;
o is 1, 2 or 3;
or each of the compounds in the form of one or more stereoisomers, agriculturally acceptable salts, prodrugs, tautomers, isotopic forms, N-oxides or S-oxides thereof, as an agricultural fungicide.
In a second embodiment, the present invention encompasses the use of a an heteroaryl compound of formula (I), wherein,
X, Y, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24 and R25, a, b, c, d, e, f, g, h, I, j, k, l, m, n and o are as defined in the first embodiment hereinabove; A is selected from the group consisting of:
Figure imgf000016_0001
Figure imgf000017_0001
R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37, R39, R40, R41, R42, R44, R46, R47, R48, R50, R52, R53, R55, R56, R58, R59, R60, R61, R62, R63, R65, R66, R67, R71, R72, R73, R74, R75, R76, R77, R78, R79, R80, R81, R82, R83, R84, R85, R86, R87, R88, R89, R90, R91, R93, R95, R96, R97, R98, R99, R100, R101, R102, R103, R104, R105, R106, R107, R108, R109, R110, R111and R113 are independently of each other, selected from the group consisting of H; halogen; CN; - NO2; -NH2; -OH; -SH; oxo; -C(=O)-OR14; -C(=O)-NR17R18; -C(=S)-NR19R20; - CR115(=N-OR116); unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or substituted heteroalkyl, heteroalkenyl or heteroalkynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substituted heterocycloalkyl and unsub- stituted or substituted heterocycloalkenyl;
R38, R43, R49, R51, R54, R57, R64, R68, R69, R70, R112 and R114 are independently of each other selected from the group consisting of -(CH2)aOR6; -(CH2)bC(=O)-R7; -C(=O)-(CH2)c- R8; -C(=O)-(CH2)d-OR9; -C(=O)-CR10(=CR11); -(CH2)f-O-C(=O)-R13; -(CH2)g-C(=O)- OR14; -C(=O)-O-(CH2)h-R15; -S(=O)j-R23; unsubstituted or substituted alkyl, alkenyl or alkynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloal- kenyl; unsubstituted or substituted heterocycloalkyl; and unsubstituted or substituted heterocycloalkenyl;
R115 and R116 are independently of each other selected from the group consisting of H; halogen; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubsti- tuted or substituted alkynyl; unsubstituted or unsubstituted or substituted cycloalkyl; unsub- stituted or substituted cycloalkenyl; unsubstituted or substituted heterocycloalkyl; and unsub- stituted or substituted heterocycloalkenyl; and whereby,
the alkyl are straight-chain or branched, and comprise 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms as chain links; the alkenyl are straight chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
the alkynyl are straight-chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
the heteroalkyl, heteroalkenyl and heteroalkynyl comprise 1, 2, 3, 4, 5 or 6 carbon atoms and 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from O, N(H) or S as chain links;
the alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl and heteroalkynyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -OH, -SH, -NH2, -NH(C1-C6)alkyl,-NH-CH(CH3)2, -N(C1-C6-alkyl)2, - N(C1-C6-alkyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, - C(=O)-O-phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -CH2-C(=O)-O-C1-C6-alkyl, - C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -NH-C(=O)C(CH3)3, -S(=O)-C1-C6- alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -NH-SO2-phenyl, - N(CH3)-SO2-phenyl, -C1-C6-alkyl, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phenyl)3, cy- clopropyl, cyclobutyl, cyclopentyl, cyclohexyl, oxetanyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, oxadiazolyl, thiadiazolyl, pyr- idinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; wherein, the alkyl, hetero- cycloalkyl, cycloalkyl, aryl or heteroaryl are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, propyl, iso- propyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl;
the cycloalkyl and cycloalkenyl comprises 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms as ring mem- bers;
the heterocycloalkyl and heterocycloalkenyl are 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from the group consisting of O, N(H) and S as ring members;
the cycloalkyl, cycloalkenyl, heterocycloalkyl or heterocycloalkenyl are unsubstituted or sub- stituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -C(=O)-H, -C(=O)-C1- C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phenyl, -C(=O)-NH2, -C(
Figure imgf000018_0001
C6)alkyl, -NH-C(=O)C(CH3)3, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -C1-C6-alkyl, -CF3, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thi- ophenyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and - CH2-phenyl; wherein the alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl, are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -NH2, -CF3, -OH, -SH, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, -OCH3, -O-C2H5, phenyl and -CH2-phenyl;
the aryl are mono-, bicyclic or tricyclic and comprise 6, 10 or 14 carbon atoms;
the heteroaryl are mono- or bicyclic and 5- or 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently selected from the group consisting of O, N(H) or S as ring members;
the aryl or heteroaryl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -OH, - SH, O CH3, O C2H5, NH2, NH(C1 C6)alkyl, NH CH(CH3)2, N(C1 C6 alkyl)2, N(C1 C6-al kyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phe- nyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)- NH-phenyl, -S(=O)-C1-C6-alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, - S(=O)2-NH2, -NH-SO2-phenyl, -N(CH3)-SO2-phenyl, -C1-C6-alkyl, cyclopropyl, cyclobutyl, cy- clopentyl, cyclohexyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, 1, 2, 4-oxadiazolyl, thia- diazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; wherein the alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl are themselves unsubstituted or substi- tuted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl. In one embodiment, the present invention encompasses the compounds of formula (I), wherein A is selected from the group consisting of:
Figure imgf000019_0001
Figure imgf000020_0001
wherein,
R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37, R39, R40, R41, R42, R44, R46, R47, R48, R50, R52, R53, R55, R56, R58, R59, R60, R61, R62, R63, R65, R66, R67, R71, R72, R73, R74, R75, R76, R77, R78, R79, R80, R81, R82, R83, R84, R85, R86, R87, R88, R89, R90, R91, R93, R95, R96, R97, R98, R99, R100, R101, R102, R103, R104, R105, R106, R107, R108, R109, R110, R111and R113 are independently of each other, selected from the group consisting of H; halogen; CN; - NO2; -NH2; -OH; -SH; oxo; -C(=O)-OR14; -C(=O)-NR17R18; -C(=S)-NR19R20; - CR115(=N-OR116); unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or substituted heteroalkyl, heteroalkenyl or heteroalkynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substituted heterocycloalkyl and unsub- stituted or substituted heterocycloalkenyl;
R38, R43, R49, R51, R54, R57, R64, R68, R69, R70, R112 and R114 are independently of each other selected from the group consisting of -(CH2)aOR6; -(CH2)bC(=O)-R7; -C(=O)-(CH2)c- R8; -C(=O)-(CH2)d-OR9; -C(=O)-CR10(=CR11); -(CH2)f-O-C(=O)-R13; -(CH2)g-C(=O)- OR14; -C(=O)-O-(CH2)h-R15; -S(=O)j-R23; unsubstituted or substituted alkyl, alkenyl or alkynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloal- kenyl; unsubstituted or substituted heterocycloalkyl; and unsubstituted or substituted heterocycloalkenyl;
R115 and R116 are independently of each other selected from the group consisting of H;
halogen; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substituted heterocycloalkyl; and unsubstituted or substituted heterocycloalkenyl;
wherein, the alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl and heteroalkynyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -OH, -SH, -NH2, -NH(C1-C6)alkyl,-NH-CH(CH3)2, -N(C1-C6-alkyl)2, - N(C1-C6-alkyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, - C(=O)-O-phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -CH2-C(=O)-O-C1-C6-alkyl, - C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -NH-C(=O)C(CH3)3, -S(=O)-C1-C6- alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -NH-SO2-phenyl, - N(CH3)-SO2-phenyl, -C1-C6-alkyl, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phenyl)3, cy- clopropyl, cyclobutyl, cyclopentyl, cyclohexyl, oxetanyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, oxadiazolyl, thiadiazolyl, pyr- idinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl;
the cycloalkyl, cycloalkenyl, heterocycloalkyl or heterocycloalkenyl are unsubstituted or sub- stituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -C(=O)-H, -C(=O)-C1- C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phenyl, -C(=O)-NH2, -C(=O)-NH(C1- C6)alkyl, -NH-C(=O)C(CH3)3, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -C1-C6-alkyl, -CF3, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thi- ophenyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and - CH2-phenyl;
the aryl or heteroaryl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -OH, - SH, -O-CH3, -O-C2H5, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -N(C1-C6-alkyl)2, -N(C1-C6-al- kyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phe- nyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)- NH-phenyl, -S(=O)-C1-C6-alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, - S(=O)2-NH2, -NH-SO2-phenyl, -N(CH3)-SO2-phenyl, -C1-C6-alkyl, cyclopropyl, cyclobutyl, cy- clopentyl, cyclohexyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, 1, 2, 4-oxadiazolyl, thia- diazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl. In a yet another embodiment, the present invention encompasses the use of compounds of for- mula (I), wherein,
A is selected from the group consisting of:
Figure imgf000021_0001
wherein,
R28, R29, R71, R72, R73, R74, R75, R76, R77, R78, R79, R80, R81, R82, R83, R86, R87 and R88 are independently of each other, selected from the group consisting of H; Cl; F; Br; I; CN; - NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; oxo; -C(=O)NH2; -CH(=N-OH); -CH(=N- OCH3); CH( N OCH2CH3); CH( N O(CH2)2CH3); CH( N O(CH2)4CH3); C(CH3)( N OH); -C(CH3)(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -O-CH3; -O-CH2-CH3; - O(CH2)2CH3; -O(CH2)3CH3; -O(CH2)4CH3; -O(CH2)5CH3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1-propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cyclopro- penyl; cyclobutenyl; cyclopentenyl; cyclohexenyl; oxetanyl; piperidinyl; piperazinyl; mor- pholinyl; thiomorpholinyl; 1,2,4-oxadiazolyl; 1,3,4-trimethyl piperazinyl; 2,3-dihydro- furanyl; 2,3-dihydrothienyl; 2,3-dihydropyrrolyl; 2,3-dihydroisoxazolyl and 2,3-dihy- drooxazol-2-yl; and wherein, alkyl, alkenyl and alkynyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of F, Cl, -CN, -OH, - NH2, -C(=O)-OH, -C(=O)-OCH3, -Si-(CH3)3, -Si-(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phenyl)3, phenyl and -CH2-phenyl; and wherein, the cycloalkyl, cycloalkenyl, heterocycloalkyl and heterocycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents in- dependently of each other, selected from the group consisting of 1, 2, 3, 4 or 5 substit- uents independently of each other, selected from the group consisting of F, Cl, Br, I, - CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, - C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH-C(=O)-CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl. In a yet another embodiment, the present invention encompasses the use of compounds of for- mula (I), wherein,
X is CR4;
Y is CR5; A is selected from the group consisting of:
Figure imgf000022_0001
R1 is selected from the group consisting of hydrogen; -CH2-OH; -CH2-OCH3; -CH2-O- CH(CH3)2; -CH2-O-(CH2)2-Si(CH3)3; -C(=O)-CH3; -C(=O)-CH2-CH3; -(C=O)-(CH2)2- CH3; -(C=O)-(CH2)3-CH3; -(C=O)-(CH2)3-CH3; -(C=O)-(CH2)4-CH3; -(C=O)-(CH2)5- CH3; -C(=O)-C(CH3)3; -C(=O)-CH2-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-cyclopropyl; - C(=O)-phenyl; -C(=O)-CH2-cyclopropyl; -C(=O)-CH2-phenyl; -CH2-O-(C=O)-CH3; - CH2-O-(C=O)-CH2-CH3; -CH2-O-(C=O)-(CH2)2-CH3; -CH2-O-(C=O)-(CH2)3-CH3; - CH2-O-(C=O)-(CH2)4-CH3; -CH2-O-(C=O)-(CH2)5-CH3; -CH2-O-(C=O)-C(CH3)3; -CH2- O (C O) phenyl; C( O) OCH3; C( O) OCH2 CH3; C( O) O (CH2)2 CH3; C( O) O (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3;-C(=O)-O-CH2-CH(CH3)2; - C(=O)-O-CH(CH3)2; -C(=O)-O-CH2-CCl3; -C(=O)-O-C(CH3)3; -C(=O)-O-(CH2)6-CH3; - C(=O)-O-CH2-CH=CH; -C(=O)-O-CH2-C≡CH; -C(=O)O-phenyl; -C(=O)-O-CH2-phe- nyl; -CH2-C(=O)-OCH3; -CH2-C(=O)-OCH2-CH3; -CH2-C(=O)-O(CH2)2-CH3; -CH2- C(=O)-O(CH2)3-CH3; -CH2-C(=O)-O(CH2)4-CH3; -CH2-C(=O)-O(CH2)5-CH3; -CH2- C(=O)-OC(CH3)3; -CH2-C(=O)-O-CH2-CH=CH; -CH2-C(=O)-O-CH=CH-CH3; -C(=O)- NH2; -C(=O)-NH-CH3; -C(=O)-N-(CH3)2; -C(=O)-pyridyl; -C(=O)-pyrimidinyl; -C(=S)- NH2; -C(=S)-NH-CH3; -C(=S)-N-(CH3)2; -C(=S)-pyridyl; -C(=S)-pyrimidinyl; -S(=O)2- CH3; -S(=O)2-CH2-CH3; -S(=O)2-(CH2)2-CH3; -S(=O)2-(CH2)2-CH3; -S(=O)2-tert butyl; - S(=O)2-phenyl; wherein, cyclopropyl, phenyl, pyridyl and pyrimidinyl is unsubstituted or substituted with 1, 2 or 3, substituents independently of each other selected from the group consisting of F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2;
-CF2-CF3; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -C(=O)-O- (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; - C(=O)-O-C(CH3)3; R3 is selected from the group consisting of hydrogen, Cl; F; Br; I; -CN; -O-CH3; -C(CH3)2- OH; -CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)-O-CH3; -CF2- CF3; methyl, ethenyl, isopropenyl, ethynyl and cyclopropyl; and the remaining of R4 and R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; -CF3; - CHF2; -CH(F)-CF3; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobu- tyl, isopentyl and tert butyl; or R4 is selected from the group consisting of hydrogen, F; Cl; Br and I; and the remaining of R3 and R5 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; -C(CH3)2-OH; -CHF2; -CH(F)-CF3; -CH(CF3)- OH; -C(=O)-O-CH3; -CF2-CF3; methyl, ethenyl, isopropenyl, ethynyl, and cyclopropyl; or R5 is selected from the group consisting of hydrogen, F; Cl; Br; I; CN; -CF3; -CHF2; - CH(F)-CF3; methyl; and the remaining of R3 and R4 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; -O- CH2-CH3; -C(CH3)2-OH; -CHF2; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O- C(CH3)3; -CF2-CF3; methyl, tert butyl, ethenyl, isopropenyl, ethynyl and cyclopropyl; R28, R29, R53, R55, R56, R58, R61, R62, R71, R72, R73, R74, R75, R76, R77, R78, R79, R80, R81, R82, R83, R84, R85, R86, R87 and R88 are independently of each other, selected from the group consist- ing of H; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; oxo; -C(=O)NH2; - CH(=N-OH); -CH(=N-OCH3); -CH(=N-OCH2CH3); -CH(=N-O(CH2)2CH3); -CH(=N- O(CH2)4CH3); -C(CH3)(=N-OH); -C(CH3)(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -O-CH3; O CH2 CH3; O(CH2)2CH3; O(CH2)3CH3; O(CH2)4CH3; O(CH2)5CH3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1-propenyl; isopropenyl; iso- butenyl; ethynyl; propynyl; butynyl; cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cyclo- propenyl; cyclobutenyl; cyclopentenyl; cyclohexenyl; oxetanyl; piperidinyl; piperazinyl; mor- pholinyl; thiomorpholinyl; 1,2,4-oxadiazolyl; 1,3,4-trimethyl piperazinyl; 2,3-dihydrofuranyl; 2,3-dihydrothienyl; 2,3-dihydropyrrolyl; 2,3-dihydroisoxazolyl and 2,3-dihydrooxazol-2-yl; and wherein, alkyl, alkenyl and alkynyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of F, Cl, -CN, -OH, -NH2, -C(=O)-OH, - C(=O)-OCH3, -Si-(CH3)3, -Si-(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phenyl)3, phenyl and -CH2-phe- nyl; and wherein, the cycloalkyl, cycloalkenyl, heterocycloalkyl and heterocycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)- OCH3, -NH-C(=O)-CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl;
R54 and R57 are independently of each other selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert butyl; wherein, the alkyl is unsubsti- tuted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of F, Cl, , Br, I, -CN, -CF3, -CN, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-OH, -C(=O)- OCH3, -Si-(CH3)3, -Si-(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phenyl)3, phenyl and -CH2-phenyl. In a further preferred embodiment, the present invention encompasses the use of compounds of formula (I), wherein,
X is CR4;
Y is CR5;
A is selected from the group consisting of:
Figure imgf000024_0001
R1 is selected from the group consisting of hydrogen; -CH2-OH; -CH2-OCH3; -CH2-O- CH(CH3)2; -CH2-O-(CH2)2-Si(CH3)3; -C(=O)-CH3; -C(=O)-CH2-CH3; -(C=O)-(CH2)2- CH3; -(C=O)-(CH2)3-CH3; -(C=O)-(CH2)3-CH3; -(C=O)-(CH2)4-CH3; -(C=O)-(CH2)5- CH3; -C(=O)-C(CH3)3; -C(=O)-CH2-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-cyclopropyl; - C(=O)-phenyl; -C(=O)-CH2-cyclopropyl; -C(=O)-CH2-phenyl; -CH2-O-(C=O)-CH3; - CH2-O-(C=O)-CH2-CH3; -CH2-O-(C=O)-(CH2)2-CH3; -CH2-O-(C=O)-(CH2)3-CH3; - CH2-O-(C=O)-(CH2)4-CH3; -CH2-O-(C=O)-(CH2)5-CH3; -CH2-O-(C=O)-C(CH3)3; -CH2- O (C O) phenyl; C( O) OCH3; C( O) OCH2 CH3; C( O) O (CH2)2 CH3; C( O) O (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3;-C(=O)-O-CH2-CH(CH3)2; - C(=O)-O-CH(CH3)2; -C(=O)-O-CH2-CCl3; -C(=O)-O-C(CH3)3; -C(=O)-O-(CH2)6-CH3; - C(=O)-O-CH2-CH=CH; -C(=O)-O-CH2-C≡CH; -C(=O)O-phenyl; -C(=O)-O-CH2-phe- nyl; -CH2-C(=O)-OCH3; -CH2-C(=O)-OCH2-CH3; -CH2-C(=O)-O(CH2)2-CH3; -CH2- C(=O)-O(CH2)3-CH3; -CH2-C(=O)-O(CH2)4-CH3; -CH2-C(=O)-O(CH2)5-CH3; -CH2- C(=O)-OC(CH3)3; -CH2-C(=O)-O-CH2-CH=CH; -CH2-C(=O)-O-CH=CH-CH3; -C(=O)- NH2; -C(=O)-NH-CH3; -C(=O)-N-(CH3)2; -C(=O)-pyridyl; -C(=O)-pyrimidinyl; -C(=S)- NH2; -C(=S)-NH-CH3; -C(=S)-N-(CH3)2; -C(=S)-pyridyl; -C(=S)-pyrimidinyl; -S(=O)2- CH3; -S(=O)2-CH2-CH3; -S(=O)2-(CH2)2-CH3; -S(=O)2-(CH2)2-CH3; -S(=O)2-tert butyl; - S(=O)2-phenyl; wherein, cyclopropyl, phenyl, pyridyl and pyrimidinyl is unsubstituted or substituted with 1, 2 or 3, substituents independently of each other selected from the group consisting of F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2;
-CF2-CF3; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -C(=O)-O- (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; - C(=O)-O-C(CH3)3; R3 is selected from the group consisting of hydrogen, Cl; F; Br; I; -CN; -O-CH3; -C(CH3)2- OH; -CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)-O-CH3; -CF2- CF3; methyl, ethenyl, isopropenyl, ethynyl and cyclopropyl; and the remaining of R4 and R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; -CF3; - CHF2; -CH(F)-CF3; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobu- tyl, isopentyl and tert butyl; or R4 is selected from the group consisting of hydrogen, F; Cl; Br and I; and the remaining of R3 and R5 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; -C(CH3)2-OH; -CHF2; -CH(F)-CF3; -CH(CF3)- OH; -C(=O)-O-CsH3; -CF2-CF3; methyl, ethenyl, isopropenyl, ethynyl, and cyclopro- pyl; or R5 is selected from the group consisting of hydrogen, F; Cl; Br; I; CN; -CF3; -CHF2; - CH(F)-CF3; methyl; and the remaining of R3 and R4 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; -O- CH2-CH3; -C(CH3)2-OH; -CHF2; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O- C(CH3)3; -CF2-CF3; methyl, tert butyl, ethenyl, isopropenyl, ethynyl and cyclopropyl; R28, R29, R71, R72, R73, R74, R75, R76, R77, R78, R79, R80, R81, R82, R83, R87 and R88 are independently of each other, selected from the group consisting of H; Cl; F; Br; I; CN; -NO2; -NH2; -NH- CH3; -N(CH3)2; -OH; -SH; oxo; -C(=O)NH2; -CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; - CH=C(CN)2; -O-CH3; -O(CH2)5CH3; -CF3; methyl; ethynyl; propynyl; butynyl; cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cyclopropenyl; cyclobutenyl; cyclopentenyl; cyclohex enyl; oxetanyl; piperidinyl; piperazinyl; morpholinyl; thiomorpholinyl; 1,2,4-oxadiazolyl. In a further preferred embodiment, the present invention encompasses the use of compounds of formula (I), wherein,
X is CR4;
Y is CR5;
A is selected from the group consisting of:
Figure imgf000026_0001
R1 is hydrogen; R2 is hydrogen; R3 is selected from the group consisting of hydrogen, Cl; F; Br; I; -CN; -O-CH3; -C(CH3)2-OH; - CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)-O-CH3; -CF2-CF3; methyl, ethenyl, isopropenyl, ethynyl and cyclopropyl; and the remaining of R4 and R5 are inde- pendently of each other selected from hydrogen; or R4 is hydrogen; and the remaining of R3 and R5 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; -C(CH3)2-OH; -CHF2; - CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -CF2-CF3; methyl, ethenyl, isopropenyl, ethynyl, and cyclopropyl; R28, R29, R71, R72, R73, R74, R75, R76, R77, R78, R79, R80, R81, R82, R83, R87 and R88 are independently of each other, selected from the group consisting of H; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; - N(CH3)2; -OH; -SH; oxo; -C(=O)NH2; -CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -O-CH3; -O(CH2)5CH3; -CF3; methyl; ethynyl; propynyl; butynyl; cyclopropyl; cyclobutyl; cyclopen- tyl; cyclohexyl; cyclopropenyl; cyclobutenyl; cyclopentenyl; cyclohexenyl; oxetanyl; piperidinyl; pi- perazinyl; morpholinyl; thiomorpholinyl; 1,2,4-oxadiazolyl. In another embodiment, the present invention encompasses the use of compounds of formula (I), wherein R1 is selected from the group consisting of hydrogen; -CH2-OH; -CH2-OCH3; -CH2-O- CH(CH3)2; -CH2-O-(CH2)2-Si(CH3)3; -C(=O)-CH3; -C(=O)-CH2-CH3; -(C=O)-(CH2)2- CH3; (C O) (CH2)3 CH3; (C O) (CH2)3 CH3; (C O) (CH2)4 CH3; (C O) (CH2)5 CH3; -C(=O)-C(CH3)3; -C(=O)-CH2-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-cyclopropyl; - C(=O)-phenyl; -C(=O)-CH2-cyclopropyl; -C(=O)-CH2-phenyl; -CH2-O-(C=O)-CH3; - CH2-O-(C=O)-CH2-CH3; -CH2-O-(C=O)-(CH2)2-CH3; -CH2-O-(C=O)-(CH2)3-CH3; - CH2-O-(C=O)-(CH2)4-CH3; -CH2-O-(C=O)-(CH2)5-CH3; -CH2-O-(C=O)-C(CH3)3; -CH2- O-(C=O)-phenyl; -C(=O)-OCH3; -C(=O)-OCH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O- (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3;-C(=O)-O-CH2-CH(CH3)2; - C(=O)-O-CH(CH3)2; -C(=O)-O-CH2-CCl3; -C(=O)-O-C(CH3)3; -C(=O)-O-(CH2)6-CH3; - C(=O)-O-CH2-CH=CH; -C(=O)-O-CH2-C≡CH; -C(=O)O-phenyl; -C(=O)-O-CH2-phe- nyl; -CH2-C(=O)-OCH3; -CH2-C(=O)-OCH2-CH3; -CH2-C(=O)-O(CH2)2-CH3; -CH2- C(=O)-O(CH2)3-CH3; -CH2-C(=O)-O(CH2)4-CH3; -CH2-C(=O)-O(CH2)5-CH3; -CH2- C(=O)-OC(CH3)3; -CH2-C(=O)-O-CH2-CH=CH; -CH2-C(=O)-O-CH=CH-CH3; -C(=O)- NH2; -C(=O)-NH-CH3; -C(=O)-N-(CH3 ) 2; -C(=O)-pyridyl; -C(=O)-pyrimidinyl; -C(=S)- NH2; -C(=S)-NH-CH3; -C(=S)-N-(CH3 ) 2; -C(=S)-pyridyl; -C(=S)-pyrimidinyl; -S(=O)2- CH3; -S(=O)2-CH2-CH3; -S(=O)2-(CH2)2-CH3; -S(=O)2-(CH2)2-CH3; -S(=O)2-tert butyl; - S(=O)2-phenyl; wherein, cyclopropyl, phenyl, pyridyl and pyrimidinyl is unsubstituted or substituted with 1, 2 or 3, substituents independently of each other selected from the group consisting of F, Cl, Br, I and -NO2.
In a yet another embodiment, the present invention encompasses the use of compounds of for- mula (I), wherein R1 is selected from the group consisting of hydrogen; -CH2-OH; -CH2-OCH3; -CH2-O- CH(CH3)2; -CH2-O-(CH2)2-Si(CH3)3; -C(=O)-CH3; -C(=O)-CH2-CH3; -C(=O)-C(CH3)3; -C(=O)-CH2-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-cyclopropyl; -C(=O)-phenyl; -C(=O)- CH2-phenyl; -CH2-O(C=O)-CH2-CH3; -CH2-O-(C=O)-C(CH3)3; -CH2-O-(C=O)-phenyl; -C(=O)-OCH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-CH2-CH(CH3)2; -C(=O)-O-CH(CH3)2; - C(=O)-O-CH2-CCl3; -C(=O)-O-C(CH3)3; -C(=O)-O-(CH2)6-CH3; -C(=O)-O-CH2- CH=CH; -C(=O)-O-CH2-C≡CH; -C(=O)O-phenyl; -C(=O)-O-CH2-phenyl; -CH2-C(=O)- OCH3; -CH2-C(=O)-OCH2-CH3; -CH2-C(=O)-OC(CH3)3; -CH2-C(=O)-O-CH2-CH=CH; S(O)2-CF3; -S(O)2-phenyl; -S-phenyl; -C(=O)-NH2 and -C(=O)-N(CH3)2; wherein, cy- clopropyl, phenyl, pyridyl and pyrimidinyl is unsubstituted or substituted with 1, 2 or 3, substituents independently of each other selected from the group consisting of F, Cl, Br, I and -NO2.
In a further embodiment, the present invention encompasses the use of compounds of formula (I), wherein, R1 is hydrogen. In a yet further embodiment, the present invention encompasses the use of compounds of formula
(I), wherein, R1 is -CH2-OH; -CH2-OCH3; -CH2-O-CH(CH3)2; -CH2-O-(CH2)2-Si(CH3)3; -C(=O)-CH3; - C(=O)-CH2-CH3; -C(=O)-C(CH3)3; -C(=O)-CH2-OCH3; -C(=O)-CH=CH-CH3; -C(=O)- cyclopropyl; -C(=O)-phenyl; -C(=O)-CH2-phenyl; -CH2-O-(C=O)-C(CH3)3; -CH2-O- (C=O)-phenyl; -C(=O)-OCH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-CH2-CH(CH3)2; - C( O) O CH(CH3)2; C( O) O CH2 CCl3; C( O) O C(CH3)3; C( O) O (CH2)6 CH3; C(=O)-O-CH2-CH=CH; -C(=O)-O-CH2-C≡CH; -C(=O)O-phenyl; -C(=O)-O-CH2-phe- nyl; -CH2-C(=O)-OCH3; -CH2-C(=O)-OCH2-CH3; -CH2-C(=O)-OC(CH3)3; -CH2-C(=O)- O-CH2-CH=CH and -C(=O)-NH2; ; wherein, cyclopropyl, phenyl, pyridyl and pyrimidi- nyl is unsubstituted or substituted with 1, 2 or 3, substituents independently of each other selected from the group consisting of F, Cl, Br, I and -NO2.
In one embodiment, the present invention encompasses the use of compounds of formula (I), wherein
R2 is selected from the group consisting of hydrogen; halogen; CN; -C(=O)-OR14; unsub- stituted or substituted alkyl; unsubstituted or substituted cycloalkyl and unsubstituted or substituted cycloalkenyl; wherein, alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN, -OH, -SH, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -N(C1-C6-alkyl)2, - N(C1-C6-alkyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-al- kyl, -C(=O)-O-phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -CH2-C(=O)-O-C1- C6-alkyl, -C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -NH-C(=O)- C(CH3)3, -S(=O)-C1-C6-alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, - S(=O)2-NH2, -NH-SO2-phenyl, -N(CH3)-SO2-phenyl, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2- phenyl, -Si-(phenyl)3, phenyl and -CH2-phenyl; wherein, the cycloalkyl or cycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, - CH2-C(=O)-OCH3, -NH-C(=O)-CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopro- pyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl;
R14 is selected from the group consisting of hydrogen; halogen; CN; unsubstituted or sub- stituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; un- substituted or substituted aryl; unsubstituted or substituted -(alkylene)-aryl; unsubsti- tuted or substituted heterocycloalkyl; unsubstituted or substituted heterocycloalkenyl; unsubstituted or substituted heteroaryl; wherein, alkyl, alkenyl and alkynyl is unsubsti- tuted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of wherein alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of Cl, F, Br, I, CN, -OH, - SH, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phe- nyl, -CH2-C(=O)-OH, -CH2-C(=O)-O-C1-C6-alkyl, -C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -Si-(CH3)3, - Si(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phenyl)3, phenyl and -CH2-phenyl; and wherein, the cycloalkyl or cycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substitu- ents independently of each other, selected from the group consisting of F, Cl, Br, I, - CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, - C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH-C(=O)-CH3, -NH-C(=O)- C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2- phenyl; and wherein, the heterocycloalkyl and heterocycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, CN, CF3, OH, NH2, O CF3, SH, O CH3, O C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phe- nyl.
In another embodiment, the present invention encompasses the use of compounds of formula (I), wherein
R2 is selected from the group consisting of hydrogen; halogen; CN; -C(=O)-OR14; unsub- stituted or substituted alkyl; unsubstituted or substituted cycloalkyl and unsubstituted or substituted cycloalkenyl; wherein, alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN, -OH, -SH, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -N(C1-C6-alkyl)2, - N(C1-C6-alkyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-al- kyl, -C(=O)-O-phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -CH2-C(=O)-O-C1- C6-alkyl, -C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -NH-C(=O)- C(CH3)3, -S(=O)-C1-C6-alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, - S(=O)2-NH2, -NH-SO2-phenyl, -N(CH3)-SO2-phenyl, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2- phenyl, -Si-(phenyl)3, phenyl and -CH2-phenyl; wherein, the cycloalkyl or cycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, - CH2-C(=O)-OCH3, -NH-C(=O)-CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopro- pyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl.
In a yet another embodiment, the present invention encompasses the use of compounds of for- mula (I), wherein
R2 is selected from the group consisting of hydrogen; halogen; CN; -C(=O)-OR14; unsub- stituted or substituted alkyl; unsubstituted or substituted cycloalkyl and unsubstituted or substituted cycloalkenyl; wherein, alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN, -OH, -SH, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -N(C1-C6-alkyl)2, - N(C1-C6-alkyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-al- kyl, -C(=O)-O-phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -CH2-C(=O)-O-C1- C6-alkyl, -C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -NH-C(=O)- C(CH3)3, -S(=O)-C1-C6-alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, - S(=O)2-NH2, -NH-SO2-phenyl, -N(CH3)-SO2-phenyl, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2- phenyl, -Si-(phenyl)3, phenyl and -CH2-phenyl; wherein, the cycloalkyl or cycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, - CH2-C(=O)-OCH3, -NH-C(=O)-CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopro- pyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl.
In a yet another embodiment, the present invention encompasses the use of compounds of formula (I), wherein R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -C(=O)-O-CH3; - C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4- CH3; C( O) O (CH2)5 CH3; C( O) O CH(CH3)2; C( O) O C(CH3)3; methyl, ethyl, propyl, butyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl, tert butyl, cyclopropyl, cyclo- butyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohex- enyl; wherein alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN, - OH, -SH, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -N(C1-C6-alkyl)2, -N(C1-C6-alkyl)-phe- nyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phe- nyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -CH2-C(=O)-O-C1-C6-alkyl, -C(=O)- NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -NH-C(=O)-C(CH3)3, -S(=O)-C1-C6- alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -NH-SO2- phenyl, -N(CH3)-SO2-phenyl, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phenyl)3, phenyl and -CH2-phenyl; wherein, the cycloalkyl or cycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O- C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)- OCH3, -NH-C(=O)-CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl.
In a specific embodiment, the present invention encompasses the compounds of formula (I), wherein, R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2;
-CF2-CF3; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -C(=O)-O- (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2 and - C(=O)-O-C(CH3)3.
In one embodiment, the present invention encompasses the compounds of formula (I), wherein, R3 is selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -OCH3; -C(=O)-O- CH3; methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, ethenyl, propenyl, bu- tenyl, isopropenyl, isobutenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cy- clopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, ox- etanyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, 1,2,4-oxadiazolyl, 1,3,4- trimethyl piperazinyl, 2,3-dihydrofuranyl, 2,3-dihydrothienyl, 2,3-dihydropyrrolyl, 2,3- dihydroisoxazolyl, 1,4-dihydropyridin-1-yl, dihydropyranyl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihy- drooxazol-2-yl, 3,4-dihydrooxazol-3-yl and 3,4-dihydrooxazol-4-yl; wherein, alkyl, alkenyl and alkynyl are independently of each other unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group con- sisting of Cl, Br, F, I, CN; -OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -NO2; -NH2; - NH(CH3)2; wherein, the cycloalkyl, cycloalkenyl, heterocycloalkyl and heterocycloal- kenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O- phenyl, -CH2-C(=O)-OCH3, -NH-C(=O)-CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, pro- pyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl.
In another embodiment, the present invention encompasses the use of compounds of formula (I), wherein, R3 is selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -O-CH3; -O-CH2- CH3; -C(=O)-O-CH3; methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, ethynyl, propynyl, butynyl, cyclopropyl, cy- clobutyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl and cy- clohexenyl; wherein, alkyl, alkenyl or alkynyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -NO2; -NH2; -NH(CH3)2; wherein, the cycloalkyl and cycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, -CH2-C(=O)- OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH-C(=O)-CH3, -NH-C(=O)- C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2- phenyl.
In a yet another embodiment, the present invention encompasses the use of compounds of formula (I), wherein,
R3 is selected from the group consisting of hydrogen, Cl; F; Br; I; -CN; -O-CH3; -O-CH2- CH3; -C(CH3)2-OH; -CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)- O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)- O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CF2-CF3; methyl, ethyl, propyl, butyl, isopropyl, iso- butyl, tert butyl, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
In a specific embodiment, the present invention encompasses the use of compounds of formula (I), wherein,
R3 is selected from the group consisting of hydrogen, Cl; F; Br; I; -CN; -O-CH3; -O-CH2- CH3; -C(CH3)2-OH; -CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)- O-CH3; -CF2-CF3; methyl, ethenyl, isopropenyl, ethynyl and cyclopropyl. In one embodiment, the present invention encompasses the use of compounds of formula (I), wherein, R4 is selected from the group consisting of hydrogen and halogen. In a specific embodiment, the present invention encompasses the use of compounds of formula (I), wherein, R4 is selected from the group consisting of hydrogen, F; Cl; Br and I. In one embodiment, the present invention encompasses the use of compounds of formula (I) wherein, R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; methyl, ethyl, pro- pyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, tetrahydro- furanyl, tetrahydrothiophenyl, tetrahydropyranyl, oxetanyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, 1,2,4 oxadiazolyl, 1,3,4 trimethyl piperazinyl, 2,3 dihy drofuranyl, 2,3-dihydrothienyl, 2,3-dihydropyrrolyl, 2,3-dihydroisoxazolyl, 1,4-dihydro- pyridin-1-yl, dihydropyranyl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihy- drooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl and 3,4-dihydrooxazol-4-yl; wherein, alkyl and alkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2; -CF2-CF3; -C(=O)-O-CH3; -C(=O)-O- CH2-CH3; -NO2; -NH2 and -NH(CH3)2; and wherein, the cycloalkyl, cycloalkenyl, het- erocycloalkyl and heterocycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl.
In another embodiment, the present invention encompasses the use of compounds of formula (I), wherein, R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; methyl, ethyl, pro- pyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl; wherein, alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of Cl, Br, F, I, CN; -CF3; - CCl3; -CHF2; -CF2-CF3; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -NO2; -NH2; -NH(CH3)2; and wherein, the cycloalkyl and cycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consist- ing of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl.
In a specific embodiment, the present invention encompasses the use of compounds of formula (I), wherein,
R5 is selected from the group consisting of hydrogen, F; Cl; Br; I; CN; -CF3; -CHF2; - CH(F)-CF3; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, iso- pentyl and tert butyl.
In another embodiment, the present invention encompasses the use of compounds of formula (I), wherein, R3 is selected from the group consisting of hydrogen, Cl; F; Br; I; -CN; -O-CH3; -O-CH2- CH3; -C(CH3)2-OH; -CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)- O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)- O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CF2-CF3; methyl, ethyl, propyl, butyl, isopropyl, iso- butyl, tert butyl, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; and the remaining of R4 and R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl and tert butyl; or R is selected from the group consisting of hydrogen, F; Cl; Br and I; and the remaining of R3 and R5 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; -O-CH2-CH3; -C(CH3)2-OH; -CHF2; -CH(F)- CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; - C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CF2-CF3; methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, ethenyl, propenyl, butenyl, isopro- penyl, isobutenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; or R5 is selected from the group consisting of hydrogen, F; Cl; Br; I; CN; -CF3; -CHF2; - CH(F)-CF3; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, iso- pentyl and tert butyl; and the remaining of R3 and R4 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; -O- CH2-CH3; -C(CH3)2-OH; -CHF2; -CH(F)-CF3; -CH(CH3)2-OH; -CH(CF3)-OH; -C(=O)-O- CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O- CH(CH3)2; -C(=O)-O-C(CH3)3; -CF2-CF3; methyl, ethyl, propyl, butyl, isopropyl, isobu- tyl, tert butyl, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
In a further embodiment, the present invention encompasses the use of compounds of formula (I), wherein, R3 is selected from the group consisting of hydrogen, Cl; F; Br; I; -CN; -O-CH3; -C(CH3)2- OH; -CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)-O-CH3; -CF2- CF3; methyl, ethenyl, isopropenyl, ethynyl and cyclopropyl; and the remaining of R4 and R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; -CF3; - CHF2; -CH(F)-CF3; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobu- tyl, isopentyl and tert butyl; or R4 is selected from the group consisting of hydrogen, F; Cl; Br and I; and the remaining of R3 and R5 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; -C(CH3)2-OH; -CHF2; -CH(F)-CF3; -CH(CF3)- OH; -C(=O)-O-CH3; -CF2-CF3; methyl, ethenyl, isopropenyl, ethynyl, and cyclopropyl; or R5 is selected from the group consisting of hydrogen, F; Cl; Br; I; CN; -CF3; -CHF2; - CH(F)-CF3; methyl; and the remaining of R3 and R4 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; -O- CH2-CH3; -C(CH3)2-OH; -CHF2; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O- C(CH3)3; -CF2-CF3; methyl, tert butyl, ethenyl, isopropenyl, ethynyl and cyclopropyl. In a further specific embodiment, the present invention encompasses the use of compounds of formula (I), wherein, R is selected from the group consisting of hydrogen, Cl; F; Br; I; CN; O CH3; C(CH3)2 OH; -CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)-O-CH3; -CF2- CF3; and the remaining of R4 and R5 is selected from the group consisting of hydrogen; -CHF2; -CH(F)-CF3 and methyl; or R4 is hydrogen; and the remaining of R3 and R5 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; -C(CH3)2-OH; - CHF2; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3 and -CF2-CF3; or R5 is selected from the group consisting of hydrogen, -CHF2; -CH(F)-CF3; methyl; and the remaining of R3 and R4 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; -C(CH3)2-OH; -CHF2; -CH(F)- CF3; -CH(CF3)-OH; -C(=O)-O-CH3 and -CF2-CF3.
In a yet further specific embodiment, the present invention encompasses the use of compounds of formula (I), wherein, R3 is selected from the group consisting of hydrogen, Cl; F; Br; I; -CN; -O-CH3; -C(CH3)2- OH; -CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)-O-CH3; -CF2- CF3; and the remaining of R4 and R5 independently of each other is selected from hydrogen; or R4 is hydrogen; and the remaining of R3 and R5 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; -C(CH3)2-OH; - CHF2; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3 and -CF2-CF3; or R5 is hydrogen; and the remaining of R3 and R4 are independently of each other is se- lected from the group consisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; -C(CH3)2- OH; -CHF2; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3 and -CF2-CF3.
In a further embodiment, the present invention encompasses the use of compounds of formula (I), wherein, R3 is selected from the group consisting of hydrogen, methyl, ethenyl, isopropenyl, ethynyl and cyclopropyl; and the remaining of R4 and R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; -CF3; -CHF2; -CH(F)-CF3; methyl, ethyl, pro- pyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl and tert butyl; or R is selected from the group consisting of hydrogen, F; Cl; Br and I; and the remaining of R3 and R5 are independently of each other selected from the group consisting of methyl, ethenyl, isopropenyl, ethynyl, and cyclopropyl; or R5 is selected from the group consisting of hydrogen, F; Cl; Br; I; F; Cl; Br; I; CN; -CF3;
-CHF2; -CH(F)-CF3; methyl and the remaining of R3 and R4 are independently of each other is selected from the group consisting of hydrogen; methyl, ethenyl, iso- propenyl, ethynyl and cyclopropyl.
In a further specific embodiment, the present invention encompasses the use of compounds of formula (I), wherein, R3 is selected from the group consisting of hydrogen, methyl, ethenyl, isopropenyl, ethynyl and cyclopropyl; and the remaining of R4 and R5 are independently of each other selected from the group consisting of hydrogen; or R4 is hydrogen; and the remaining of R3 and R5 are independently of each other selected from the group consisting of methyl, ethenyl, isopropenyl, ethynyl, and cyclopropyl; or R5 is hydrogen; and the remaining of R3 and R4 are independently of each other is se- lected from the group consisting of hydrogen; methyl, ethenyl, isopropenyl, ethynyl and cyclopropyl.
In one embodiment, the present invention encompasses the use of compounds of formula (I), wherein,
R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24 and R25 are independently of each other, selected from the group consisting of hydrogen; halogen; CN; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or substituted cycloalkyl; unsubsti- tuted or substituted cycloalkenyl; unsubstituted or substituted aryl; unsubstituted or substituted -(alkylene)-aryl; unsubstituted or substituted heterocycloalkyl; unsubsti- tuted or substituted heterocycloalkenyl; unsubstituted or substituted heteroaryl;
wherein,
the alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl and heteroalkynyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -OH, -SH, -NH2, -NH(C1-C6)alkyl,-NH-CH(CH3)2, -N(C1-C6-alkyl)2, - N(C1-C6-alkyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, - C(=O)-O-phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -CH2-C(=O)-O-C1-C6-alkyl, - C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -NH-C(=O)C(CH3)3, -S(=O)-C1-C6- alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -NH-SO2-phenyl, - N(CH3)-SO2-phenyl, -C1-C6-alkyl, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phenyl)3, cy- clopropyl, cyclobutyl, cyclopentyl, cyclohexyl, oxetanyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, oxadiazolyl, thiadiazolyl, pyr idinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl;
the cycloalkyl, cycloalkenyl, heterocycloalkyl or heterocycloalkenyl are unsubstituted or sub- stituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -C(=O)-H, -C(=O)-C1- C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phenyl, -C(=O)-NH2, -C(=O)-NH(C1- C6)alkyl, -NH-C(=O)C(CH3)3, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -C1-C6-alkyl, -CF3, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thi- ophenyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and - CH2-phenyl;
the aryl or heteroaryl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -OH, - SH, -O-CH3, -O-C2H5, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -N(C1-C6-alkyl)2, -N(C1-C6-al- kyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phe- nyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)- NH-phenyl, -S(=O)-C1-C6-alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, - S(=O)2-NH2, -NH-SO2-phenyl, -N(CH3)-SO2-phenyl, -C1-C6-alkyl, cyclopropyl, cyclobutyl, cy- clopentyl, cyclohexyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, 1, 2, 4-oxadiazolyl, thia- diazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl.
In another embodiment, the present invention encompasses the use of compounds of formula (I), wherein,
R6 R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24 and R25 is selected from the group consisting of hydrogen; Cl, F, Br, I, NH2, -NH-CH3, -N(CH3)2, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, tert butyl, ethenyl, pro- penyl, butenyl, isopropenyl, isopentenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobu- tyl, cyclopentyl, cyclohexyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, oxadiazolyl, thi- adiazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; wherein, the alkyl, alkenyl and alkynyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substitu- ents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, - CF3, -OH, -NO2; -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -Si-(CH3)3 and phenyl; and wherein, the cycloalkyl, heterocycloalkyl, aryl or heteroaryl are themselves unsubstituted or substi- tuted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NO2; -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, me- thyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl and phenyl.
In a yet another embodiment, the present invention encompasses the use of compounds of for- mula (I), wherein,
R6 R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24 and R25 is selected from the group consisting of hydrogen; Cl, F, Br, I, NH2, -NH-CH3, -N(CH3)2, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, tert butyl, ethynyl, cyclopropyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; wherein, the alkyl, alkenyl and alkynyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, - NO2; -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -Si-(CH3)3 and phenyl; and wherein, the cycloal- kyl, heterocycloalkyl, aryl or heteroaryl are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NO2; -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, tertiary butyl and phenyl.
In a third embodiment, the present invention encompasses the use of compounds of formula (I), wherein
X denotes CR4 and Y denotes CR5; or
X denotes N and Y denotes CR5; or
X denotes CR4 and Y denotes N; or
X denotes N and Y denotes N;
A is as defined in the second embodiment; R1 is selected from the group consisting of hydrogen; -CH2-OH; -CH2-OCH3; -CH2-O- CH(CH3)2; -CH2-O-(CH2)2-Si(CH3)3; -C(=O)-CH3; -C(=O)-CH2-CH3; -(C=O)-(CH2)2- CH3; -(C=O)-(CH2)3-CH3; -(C=O)-(CH2)3-CH3; -(C=O)-(CH2)4-CH3; -(C=O)-(CH2)5- CH3; -C(=O)-C(CH3)3; -C(=O)-CH2-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-cyclopropyl; - C(=O)-phenyl; -C(=O)-CH2-cyclopropyl; -C(=O)-CH2-phenyl; -CH2-O-(C=O)-CH3; - CH2-O-(C=O)-CH2-CH3; -CH2-O-(C=O)-(CH2)2-CH3; -CH2-O-(C=O)-(CH2)3-CH3; - CH2-O-(C=O)-(CH2)4-CH3; -CH2-O-(C=O)-(CH2)5-CH3; -CH2-O-(C=O)-C(CH3)3; -CH2- O-(C=O)-phenyl; -C(=O)-OCH3; -C(=O)-OCH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O- (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3;-C(=O)-O-CH2-CH(CH3)2; - C(=O)-O-CH(CH3)2; -C(=O)-O-CH2-CCl3; -C(=O)-O-C(CH3)3; -C(=O)-O-(CH2)6-CH3; - C(=O)-O-CH2-CH=CH; -C(=O)-O-CH2-C≡CH; -C(=O)O-phenyl; -C(=O)-O-CH2-phe- nyl; -CH2-C(=O)-OCH3; -CH2-C(=O)-OCH2-CH3; -CH2-C(=O)-O(CH2)2-CH3; -CH2- C(=O)-O(CH2)3-CH3; -CH2-C(=O)-O(CH2)4-CH3; -CH2-C(=O)-O(CH2)5-CH3; -CH2- C(=O)-OC(CH3)3; -CH2-C(=O)-O-CH2-CH=CH; -CH2-C(=O)-O-CH=CH-CH3; -C(=O)- NH2; -C(=O)-NH-CH3; -C(=O)-N-(CH3)2; -C(=O)-pyridyl; -C(=O)-pyrimidinyl; -C(=S)- NH2; -C(=S)-NH-CH3; -C(=S)-N-(CH3)2; -C(=S)-pyridyl; -C(=S)-pyrimidinyl; -S(=O)2- CH3; -S(=O)2-CH2-CH3; -S(=O)2-(CH2)2-CH3; -S(=O)2-(CH2)2-CH3; -S(=O)2-tert butyl; - S(=O)2-phenyl; wherein, cyclopropyl, phenyl, pyridyl and pyrimidinyl is unsubstituted or substituted with 1, 2 or 3, substituents independently of each other selected from the group consisting of F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -C(=O)-O-CH3; - C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4- CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; methyl, ethyl, propyl, butyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl, tert butyl, cyclopropyl, cyclo- butyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohex- enyl; wherein alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN, - OH, -SH, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -N(C1-C6-alkyl)2, -N(C1-C6-alkyl)-phe- nyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phe- nyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -CH2-C(=O)-O-C1-C6-alkyl, -C(=O)- NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -NH-C(=O)-C(CH3)3, -S(=O)-C1-C6- alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -NH-SO2- phenyl, -N(CH3)-SO2-phenyl, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phenyl)3, phenyl and CH2 phenyl; wherein, the cycloalkyl or cycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O- C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)- OCH3, -NH-C(=O)-CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R3 is selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -OCH3; -C(=O)-O- CH3; -C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O- (CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, ethenyl, propenyl, butenyl, isopro- penyl, isobutenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopentyl, cy- clohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, oxetanyl, piperi- dinyl, piperazinyl, morpholinyl, thiomorpholinyl, 1,2,4-oxadiazolyl, 1,3,4-trimethyl pi- perazinyl, 2,3-dihydrofuranyl, 2,3-dihydrothienyl, 2,3-dihydropyrrolyl, 2,3-dihydroisox- azolyl, 1,4-dihydropyridin-1-yl, dihydropyranyl, 2,3-dihydrooxazol-2-yl, 2,3-dihydroox- azol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4- dihydrooxazol-3-yl and 3,4-dihydrooxazol-4-yl; wherein, alkyl, alkenyl and alkynyl are independently of each other unsubstituted or substituted with 1, 2, 3, 4 or 5 substitu- ents independently of each other selected from the group consisting of Cl, Br, F, I, CN; -OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -NO2; -NH2; -NH(CH3)2; wherein, the cycloalkyl, cycloalkenyl, heterocycloalkyl and heterocycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O- C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)- OCH3, -NH-C(=O)-CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R4 is selected from the group consisting of hydrogen; F; Cl; Br and I; R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; methyl, ethyl, pro- pyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, tetrahydro- furanyl, tetrahydrothiophenyl, tetrahydropyranyl, oxetanyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, 1,2,4-oxadiazolyl, 1,3,4-trimethyl piperazinyl, 2,3-dihy- drofuranyl, 2,3-dihydrothienyl, 2,3-dihydropyrrolyl, 2,3-dihydroisoxazolyl, 1,4-dihydro- pyridin-1-yl, dihydropyranyl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihy- drooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl and 3,4-dihydrooxazol-4-yl; wherein, alkyl and alkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2; -CF2-CF3; -C(=O)-O-CH3; -C(=O)-O- CH2-CH3; -NO2; -NH2 and -NH(CH3)2; and wherein, the cycloalkyl, cycloalkenyl, het- erocycloalkyl and heterocycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, CN, CF3, OH, NH2, O CF3, SH, O CH3, O C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37, R39, R40, R41, R42, R44, R46, R47, R48, R50, R52, R53, R55, R56, R58, R59, R60, R61, R62, R63, R65, R66, R67, R71, R72, R73, R74, R75, R76, R77, R78, R79, R80, R81, R82, R83, R84, R85, R86, R87, R88, R89, R90, R91, R93, R95, R96, R97, R98, R99, R100, R101, R102, R103, R104, R105, R106, R107, R108, R109, R110, R111 and R113 are independently of each other, selected from the group consisting of H; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; oxo; -C(=O)NH2; -CH(=N-OH); - CH(=N-OCH3); -CH(=N-OCH2CH3); -CH(=N-O(CH2)2CH3); -CH(=N-O(CH2)4CH3); - C(CH3)(=N-OH); -C(CH3)(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -O-CH3; -O-CH2- CH3; -O(CH2)2CH3; -O(CH2)3CH3; -O(CH2)4CH3; -O(CH2)5CH3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1-propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cyclopropenyl; cyclobutenyl; cyclopentenyl; cyclohexenyl; oxetanyl; piperidinyl; piper- azinyl; morpholinyl; thiomorpholinyl; 1,2,4-oxadiazolyl; 1,3,4-trimethyl piperazinyl; 2,3-dihydrofuranyl; 2,3-dihydrothienyl; 2,3-dihydropyrrolyl; 2,3-dihydroisoxazolyl and 2,3-dihydrooxazol-2-yl; and wherein, alkyl, alkenyl and alkynyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of F, Cl, -CN, -OH, -NH2, -C(=O)-OH, -C(=O)-OCH3, -Si-(CH3)3, -Si-(C2H5)3, -Si-(CH3)2-phe- nyl, -Si-(phenyl)3, phenyl and -CH2-phenyl; and wherein, the cycloalkyl, cycloalkenyl, heterocycloalkyl and heterocycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group con- sisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)- CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH-C(=O)- CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl;
R38, R43, R49, R51, R54, R57, R64, R68, R69, R70, R112 and R114 are independently of each other selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert butyl; wherein, the alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of F, Cl, , Br, I, -CN, -CF3, -CN, -OH, -NH2, -O-CF3, -SH, -O- CH3, -O-C2H5, -C(=O)-OH, -C(=O)-OCH3, -Si-(CH3)3, -Si-(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phenyl)3, phenyl and -CH2-phenyl.
In a further embodiment, the present invention encompasses the use of the compounds of formula (I), wherein,
R6 R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24 and R25 is selected from the group consisting of hydrogen; Cl, F, Br, I, NH2, -NH-CH3, -N(CH3)2, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, tert butyl, ethynyl, cyclopropyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; wherein, the alkyl is unsubstituted or substituted with -Si-(CH3)3; the aryl is unsubstituted or substituted with - NO2; and wherein, the alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl is un- substituted. In one embodiment, the present invention encompasses the use of the compounds of formula (I), wherein,
R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37, R39, R40, R41, R42, R44, R46, R47, R48, R50, R52, R53, R55, R56, R58, R59, R60, R61, R62, R63, R65, R66, R67, R71, R72, R73, R74, R75, R76, R77, R78, R79, R80, R81, R82, R83, R84, R85, R86, R87, R88, R89, R90, R91, R93, R95, R96, R97, R98, R99, R100, R101, R102, R103, R104, R105, R106, R107, R108, R109, R110, R111and R113 are independently of each other, selected from the group consisting of H; halogen; CN; - NO2; -NH2; -OH; -SH; oxo; -C(=O)-OR14; -C(=O)-NR17R18; -C(=S)-NR19R20; - CR115(=N-OR116); unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or substituted heteroalkyl, heteroalkenyl or heteroalkynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substituted heterocycloalkyl and unsub- stituted or substituted heterocycloalkenyl;
R38, R43, R49, R51, R54, R57, R64, R68, R69, R70, R112 and R114 are independently of each other selected from the group consisting of -(CH2)aOR6; -(CH2)bC(=O)-R7; -C(=O)-(CH2)c- R8; -C(=O)-(CH2)d-OR9; -C(=O)-CR10(=CR11); -(CH2)f-O-C(=O)-R13; -(CH2)g-C(=O)- OR14; -C(=O)-O-(CH2)h-R15; -S(=O)j-R23; unsubstituted or substituted alkyl, alkenyl or alkynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloal- kenyl; unsubstituted or substituted heterocycloalkyl; and unsubstituted or substituted heterocycloalkenyl;
R115 and R116 are independently of each other selected from the group consisting of H; halogen; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubsti- tuted or substituted alkynyl; unsubstituted or unsubstituted or substituted cycloalkyl; unsub- stituted or substituted cycloalkenyl; unsubstituted or substituted heterocycloalkyl; and unsub- stituted or substituted heterocycloalkenyl; and whereby,
the alkyl are straight-chain or branched, and comprise 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms as chain links;
the alkenyl are straight-chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
the alkynyl are straight-chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
the heteroalkyl, heteroalkenyl and heteroalkynyl comprise 1, 2, 3, 4, 5 or 6 carbon atoms and 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from O, N(H) or S as chain links;
the alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl and heteroalkynyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -OH, -SH, -NH2, -NH(C1-C6)alkyl,-NH-CH(CH3)2, -N(C1-C6-alkyl)2, - N(C1-C6-alkyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, - C(=O)-O-phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -CH2-C(=O)-O-C1-C6-alkyl, - C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -NH-C(=O)C(CH3)3, -S(=O)-C1-C6- alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -NH-SO2-phenyl, - N(CH3)-SO2-phenyl, -C1-C6-alkyl, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phenyl)3, cy- clopropyl, cyclobutyl, cyclopentyl, cyclohexyl, oxetanyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, oxadiazolyl, thiadiazolyl, pyr idinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; wherein, the alkyl, hetero- cycloalkyl, cycloalkyl, aryl or heteroaryl are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, propyl, iso- propyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl;
the cycloalkyl and cycloalkenyl comprises 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms as ring mem- bers;
the heterocycloalkyl and heterocycloalkenyl are 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from the group consisting of O, N(H) and S as ring members;
the cycloalkyl, cycloalkenyl, heterocycloalkyl or heterocycloalkenyl are unsubstituted or sub- stituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -C(=O)-H, -C(=O)-C1- C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phenyl, -C(=O)-NH2, -C(=O)-NH(C1- C6)alkyl, -NH-C(=O)C(CH3)3, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -C1-C6-alkyl, -CF3, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thi- ophenyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and - CH2-phenyl; wherein the alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl, are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -NH2, -CF3, -OH, -SH, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, -OCH3, -O-C2H5, phenyl and -CH2-phenyl;
the aryl are mono-, bicyclic or tricyclic and comprise 6, 10 or 14 carbon atoms;
the heteroaryl are mono- or bicyclic and 5- or 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently selected from the group consisting of O, N(H) or S as ring members;
the aryl or heteroaryl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -OH, - SH, -O-CH3, -O-C2H5, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -N(C1-C6-alkyl)2, -N(C1-C6-al- kyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phe- nyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)- NH-phenyl, -S(=O)-C1-C6-alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, - S(=O)2-NH2, -NH-SO2-phenyl, -N(CH3)-SO2-phenyl, -C1-C6-alkyl, cyclopropyl, cyclobutyl, cy- clopentyl, cyclohexyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, 1, 2, 4-oxadiazolyl, thia- diazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; wherein the alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl are themselves unsubstituted or substi- tuted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl.
In another embodiment, the present invention encompasses the use of the compounds of formula (I), wherein,
R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37, R39, R40, R41, R42, R44, R46, R47, R48, R50, R52, R53, R55, R56, R58, R59, R60, R61, R62, R63, R65, R66, R67, R71, R72, R73, R74, R75, R76, R77, R78, R79, R80, R81, R82, R83, R84, R85, R86, R87, R88, R89, R90, R91, R93, R95, R96, R97, R98, R , R , R , R , R , R , R , R , R , R , R , R , R and R are inde pendently of each other, selected from the group consisting of H; Cl; F; Br; I; CN; -NO2; - NH2; -NH-CH3; -N(CH3)2; -OH; -SH; oxo; -C(=O)NH2; -CH(=N-OH); -CH(=N-OCH3); - CH(=N-OCH2CH3); -CH(=N-O(CH2)2CH3); -CH(=N-O(CH2)4CH3); -C(CH3)(=N-OH); - C(CH3)(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -O-CH3; -O-CH2-CH3; -O(CH2)2CH3; - O(CH2)3CH3; -O(CH2)4CH3; -O(CH2)5CH3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1-propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cyclopropenyl; cyclobutenyl; cyclo- pentenyl; cyclohexenyl; oxetanyl; piperidinyl; piperazinyl; morpholinyl; thiomorpholinyl; 1,2,4-oxadiazolyl; 1,3,4-trimethyl piperazinyl; 2,3-dihydrofuranyl; 2,3-dihydrothienyl; 2,3-di- hydropyrrolyl; 2,3-dihydroisoxazolyl and 2,3-dihydrooxazol-2-yl; and wherein, alkyl, alkenyl and alkynyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of F, Cl, -CN, -OH, -NH2, -C(=O)-OH, -C(=O)-OCH3, -Si-(CH3)3, -Si- (C2H5)3, -Si-(CH3)2-phenyl, -Si-(phenyl)3, phenyl and -CH2-phenyl; and wherein, the cycloal- kyl, cycloalkenyl, heterocycloalkyl and heterocycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group con- sisting of 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH-C(=O)-CH3, -NH- C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2- phenyl; R38, R43, R49, R51, R54, R57, R64, R68, R69, R70, R112 and R114 are independently of each other selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, iso- butyl, and tert butyl; wherein, the alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of F, Cl, , Br, I, -CN, -CF3, -CN, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-OH, -C(=O)-OCH3, -Si-(CH3)3, -Si-(C2H5)3, -Si- (CH3)2-phenyl, -Si-(phenyl)3, phenyl and -CH2-phenyl.
In a fourth embodiment, the present invention encompasses the use of compounds of formula (I), is a compound of formula I(A),
Figure imgf000042_0001
wherein,
X and Y are as defined as in the third embodiment hereinabove;
R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R71, R72, R73 and R74, a, b, c, d, e, f, g, h, I, j, k, l, m, n and o are as defined in the second embodiment hereinabove;
or each of the compounds in the form of one or more stereoisomers, agriculturally
acceptable salts, prodrugs, tautomers, isotopic forms, N-oxides or S-oxides thereof, as an agricultural fungicide. In another embodiment, the present invention encompasses the use of compounds of formula I(A), wherein, R1 is selected from the group consisting of hydrogen; -CH2-OH; -CH2-OCH3; -CH2-O- CH(CH3)2; -CH2-O-(CH2)2-Si(CH3)3; -C(=O)-CH3; -C(=O)-CH2-CH3; -C(=O)-(CH2)2- CH3; -C(=O)-(CH2)3-CH3; -C(=O)-(CH2)4-CH3; -C(=O)-(CH2)5-CH3;-C(=O)-C(CH3)3; - C(=O)-CH2-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-phenyl; -C(=O)-cyclopropyl; -C(=O)- CH2-cyclopropyl; -C(=O)-CH2-phenyl; -CH2-O-(C=O)-CH3; -CH2-O-(C=O)-CH2-CH3; - CH2-O-(C=O)-(CH2)3-CH3; -CH2-O-(C=O)-(CH2)4-CH3; -CH2-O-(C=O)-(CH2)5-CH3; - CH2-O-(C=O)-C(CH3)3; -CH2-O-(C=O)-phenyl; -C(=O)-OCH3; C(=O)-O-(CH2)2CH3; - C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3;-C(=O)-OCH2- CH(CH3)2; -C(=O)-OCH(CH3)2; -C(=O)-O-CH2-CCl3; -C(=O)-OC(CH3)3; -C(=O)-O- (CH2)6-CH3; -C(=O)-O-CH2-CH=CH; -C(=O)-O-CH2-C≡CH; -C(=O)O-phenyl; -C(=O)- O-CH2-phenyl; -CH2-C(=O)-OCH3; -CH2-C(=O)-OCH2-CH3; -CH2-C(=O)-O(CH2)2- CH3; -CH2-C(=O)-O(CH2)3-CH3; -CH2-C(=O)-O(CH2)4-CH3; -CH2-C(=O)-O(CH2)5-CH3; -CH2-C(=O)-OC(CH3)3; -CH2-C(=O)-O-CH2-CH=CH; -CH2-C(=O)-O-CH=CH-CH3; - C(=O)-NH2; -C(=O)-NH-CH3; -C(=O)-N-(CH3)2; -C(=O)-pyridyl; -C(=O)-pyrimidinyl; - C(=S)-NH2; -C(=S)-NH-CH3; -C(=S)-N-(CH3 ) 2; -C(=S)-pyridyl; -C(=S)-pyrimidinyl; - S(=O)2-CH3; -S(=O)2-CH2-CH3; -S(=O)2-(CH2)2-CH3; -S(=O)2-(CH2)2-CH3; -S(=O)2- tertbutyl; -S(=O)2-phenyl; wherein, cyclopropyl, phenyl, pyridyl and pyrimidinyl is un- substituted or substituted with 1, 2 or 3, substituents independently of each other se- lected from the group consisting of F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -C(=O)-O-CH3; - C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5- CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; methyl, ethyl, propyl, butyl, hexyl, hep- tyl, isopropyl, isobutyl, isopentyl, tert butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclo- hexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl; wherein alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, F, Br, I, CN, -OH, -SH, -NH2, -NH(C1- C6)alkyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O- phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-O-C1-C6-alkyl, -C(=O)-NH2, -C(=O)-NH(C1- C6)alkyl, -C(=O)-NH-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -CF3, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phenyl)3, phenyl and -CH2-phenyl; wherein, the cycloalkyl or cycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, -CH2- C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH-C(=O)-CH3, -NH- C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R3 is selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -O-CH3; -O-CH2- CH3; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3- CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O- C(CH3)3; methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl; wherein, alkyl, alkenyl or alkynyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -NO2; -NH2; -NH(CH3)2; wherein, the cy- cloalkyl and cycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substitu- ents independently of each other, selected from the group consisting of F, Cl, Br, I, - CN, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)- OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH-C(=O)-CH3, -NH-C(=O)-C(CH3)3, me- thyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R4 is selected from the group consisting of hydrogen; F; Cl; Br and I; R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; methyl, ethyl, pro- pyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl; wherein, alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of Cl, Br, F, I, CN; -CF3; - CCl3; -CHF2; -CF2-CF3; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -NO2; -NH2; -NH(CH3)2; and wherein, the cycloalkyl and cycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consist- ing of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R71, R72, R73 and R74 are independently of each other, selected from the group consisting of H; Cl; F; Br; I; -CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; -C(=O)NH2; -CH(=N- OH); -CH(=N-OCH3); -CH(=N-OCH2CH3); -CH(=N-O(CH2)2CH3); -CH(=N- O(CH2)4CH3); -C(CH3)(=N-OH); -C(CH3)(=N-OCH3); -C(=O)-O-CH3; -C(=O)-O- (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; - C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1-propenyl; isopropenyl; isobu- tenyl; ethynyl; propynyl; butynyl; cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cy- clopropenyl; cyclobutenyl; cyclopentenyl; cyclohexenyl; oxetanyl; piperidinyl; piper- azinyl; morpholinyl; thiomorpholinyl; 1,2,4-oxadiazolyl; 1,3,4-trimethyl piperazinyl; 2,3-dihydrofuranyl; 2,3-dihydrothienyl; 2,3-dihydropyrrolyl; 2,3-dihydroisoxazolyl and 2,3-dihydrooxazol-2-yl; and wherein, alkyl, alkenyl and alkynyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of F, Cl, -CN, -OH, -NH2, -C(=O)-OH, -C(=O)-OCH3, -Si-(CH3)3, -Si-(C2H5)3, -Si-(CH3)2-phe- nyl, -Si-(phenyl)3, phenyl and -CH2-phenyl; and wherein, the cycloalkyl, cycloalkenyl, heterocycloalkyl and heterocycloalkenyl are independently of each other unsubsti- tuted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, - CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH-C(=O)-CH3, - NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl. In a preferred embodiment of the fourth embodiment, the present invention encompasses the use of compounds of formula I(A), wherein, R1 is selected from the group consisting of hydrogen; -NH2; -CH2-OH; -CH2-OCH3; -CH2- O-(CH2)2-Si-(CH3)3; -C(=O)-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-O-phenyl; -C(=O)-O- CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; - C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH2-phenyl; -C(=O)-O-CH2-phenyl; -C(=O)-O-CH2- CH=CH; -C(=O)-OC(CH3)3; -CH2C(=O)-OCH3; -S(O)2-phenyl; -S(O)2-CF3; -S-phenyl and -C(=O)-NH2; wherein phenyl is substituted with F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2;
-CF2-CF3; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -C(=O)-O- (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; - C(=O)-O-C(CH3)3; R3 is selected from the group consisting of hydrogen, Cl; F; Br; I; -CN; -O-CH3; -O-CH2- CH3; -C(CH3)2-OH; -CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)- O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)- O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CF2-CF3; methyl, ethyl, propyl, butyl, isopropyl, iso- butyl, tert butyl, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; and the remaining of R4 and R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; -CF3; - CHF2; -CH(F)-CF3; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobu- tyl, isopentyl and tert butyl; or R4 is selected from the group consisting of hydrogen, F; Cl; Br and I; and the re- maining of R3 and R5 are independently of each other selected from the group con- sisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; -O-CH2-CH3; -C(CH3)2-OH; -CHF2; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4- CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CF2-CF3; me- thyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, ethenyl, propenyl, butenyl, iso- propenyl, isobutenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; or R5 is selected from the group consisting of hydrogen, F; Cl; Br; I; CN; -CF3; -CHF2;
-CH(F)-CF3; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, iso- pentyl and tert butyl; and the remaining of R3 and R4 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; -O- CH2-CH3; -C(CH3)2-OH; -CHF2; -CH(F)-CF3; -CH(CH3)2-OH; -CH(CF3)-OH; -C(=O)-O- CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O- CH(CH3)2; -C(=O)-O-C(CH3)3; -CF2-CF3; methyl, ethyl, propyl, butyl, isopropyl, isobu- tyl, tert butyl, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; R71 is selected from the group consisting of hydrogen, -NH2; F ; -NH-CH3; -N(CH3)2 and - NO2; and the remaining of R72, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; NO2; NH2; NH CH3; N(CH3)2; -OH; -SH; -C(=O)NH2; -CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); - C(CH3)(=N-OCH3); -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; - C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; - O-CH2-CH3; -CF3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1-propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclo- propyl; and 1,2,4-oxadiazolyl; or R72 is selected from the group consisting of hydrogen, F, Cl, Br and I; and the re- maining of R71, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; - C(=O)NH2; -CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); -C(CH3)(=N-OCH3); - C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; - C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; -CF3; me- thyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1- propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; and 1,2,4- oxadiazolyl; or R73 is selected from the group consisting of hydrogen, Cl; F; Br; I; -CN; -NO2; -NH2;
-NH-CH3; -N(CH3)2; -C(=O)NH2; -CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); - C(CH3)(=N-OCH3); -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; - C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; - O-CH2-CH3; -CF3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1-propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclo- propyl; and 1,2,4-oxadiazolyl; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; -NH2; -NH-CH3; - N(CH3)2; and -NO2; or R74 is selected from the group consisting of hydrogen, F; -OH; -CN and -OCH3; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; -CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; -C(=O)NH2; -CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); -C(CH3)(=N-OCH3); -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; - C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; -CF3; me- thyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1- propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; and 1,2,4- oxadiazolyl.
In a further preferred embodiment, the present invention encompasses the use of compounds of formula I(A), wherein, R1 is selected from the group consisting of hydrogen; -NH2; -CH2-OH; -CH2-OCH3; -CH2- O-(CH2)2-Si-(CH3)3; -C(=O)-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-O-phenyl; -C(=O)-O- CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; - C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH2-phenyl; -C(=O)-O-CH2-phenyl; -C(=O)-O-CH2- CH CH; C( O) OC(CH3)3; CH2C( O) OCH3; S(O)2 phenyl; S(O)2 CF3; S phenyl and -C(=O)-NH2; wherein phenyl is substituted with F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2;
-CF2-CF3; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -C(=O)-O- (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; - C(=O)-O-C(CH3)3; R3 is selected from the group consisting of hydrogen, Cl; F; Br; I; -CN; -O-CH3; -C(CH3)2- OH; -CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)-O-CH3; -CF2- CF3; methyl, ethenyl, isopropenyl, ethynyl and cyclopropyl; and the remaining of R4 and R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; -CF3; - CHF2; -CH(F)-CF3; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobu- tyl, isopentyl and tert butyl; or R4 is selected from the group consisting of hydrogen, F; Cl; Br and I; and the re- maining of R3 and R5 are independently of each other selected from the group con- sisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; -C(CH3)2-OH; -CHF2; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -CF2-CF3; methyl, ethenyl, isopropenyl, ethynyl, and cyclopropyl; R71 is selected from the group consisting of hydrogen, -NH2; F and -NO2; and the remain- ing of R72, R73 and R74 are independently of each other selected from the group con- sisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; - C(=O)NH2; -CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -O- CH2-CH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R72 is selected from the group consisting of hydrogen, F, Cl, Br and I; and the re- maining of R71, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; - C(=O)NH2; -CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R73 is selected from the group consisting of hydrogen, Cl; F; Br; I; -CN; -NO2; - C(=O)NH2; -CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; -NH2; and -NO2; or R74 is selected from the group consisting of hydrogen, F; -OH; -CN and -OCH3; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; -CN; -NO2; -OH; -SH; -C(=O)NH2; -CH(=N- OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; -CF3; me- thyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl.
In a further specific embodiment, the present invention encompasses the use of compounds of formula I (A), wherein, R is selected from the group consisting of hydrogen; NH2; CH2 OH; CH2 OCH3; CH2 O-(CH2)2-Si-(CH3)3; -C(=O)-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-O-phenyl; -C(=O)-O- CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; - C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH2-phenyl; -C(=O)-O-CH2-phenyl; -C(=O)-O-CH2- CH=CH; -C(=O)-OC(CH3)3; -CH2C(=O)-OCH3; -S(O)2-phenyl; -S(O)2-CF3; -S-phenyl and -C(=O)-NH2; wherein phenyl is substituted with F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2;
-CF2-CF3; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -C(=O)-O- (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; - C(=O)-O-C(CH3)3; R3 is selected from the group consisting of hydrogen, Cl; F; Br; I; -CN; -O-CH3; -C(CH3)2- OH; -CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)-O-CH3; -CF2- CF3; and the remaining of R4 and R5 is selected from the group consisting of hydrogen; Cl; F; Br; I; -CHF2; -CH(F)-CF3 and methyl; or R4 is hydrogen; Cl; Br; F and I; and the remaining of R3 and R5 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -CF3; - O-CH3; -C(CH3)2-OH; -CHF2; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3 and -CF2- CF3; R71 is selected from the group consisting of hydrogen, -NH2; F and -NO2; and the remain- ing of R72, R73 and R74 are independently of each other selected from the group con- sisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; - C(=O)NH2; -CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -O- CH2-CH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R72 is selected from the group consisting of hydrogen, F, Cl, Br and I; and the re- maining of R71, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; - C(=O)NH2; -CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R73 is selected from the group consisting of hydrogen, Cl; F; Br; I; -CN; -NO2; - C(=O)NH2; -CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; -NH2; and -NO2; or R74 is selected from the group consisting of hydrogen, F; -OH; -CN and -OCH3; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; -CN; -NO2; -OH; -SH; -C(=O)NH2; -CH(=N- OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; -CF3; me- thyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl. In a yet further specific embodiment, the present invention encompasses the use of compounds of formula I(A), wherein, R1 is selected from the group consisting of hydrogen; -NH2; -CH2-OH; -CH2-OCH3; -CH2- O-(CH2)2-Si-(CH3)3; -C(=O)-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-O-phenyl; -C(=O)-O- CH2-phenyl; -C(=O)-O-CH2-phenyl; -C(=O)-O-CH2-CH=CH; -C(=O)-OC(CH3)3; - CH2C(=O)-OCH3; -S(O)2-phenyl; -S(O)2-CF3; -S-phenyl and -C(=O)-NH2; wherein phenyl is substituted with F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2;
-CF2-CF3; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; R3 is selected from the group consisting of hydrogen, Cl; F; Br; I; -CN; -O-CH3; -C(CH3)2- OH; -CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)-O-CH3; -CF2- CF3; and the remaining of R4 and R5 independently of each other is selected from hydrogen; or R4 is hydrogen; and the remaining of R3 and R5 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; - C(CH3)2-OH; -CHF2; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3 and -CF2-CF3; or R5 is hydrogen; and the remaining of R3 and R4 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; - C(CH3)2-OH; -CHF2; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3 and -CF2-CF3. R71 is selected from the group consisting of hydrogen, -NH2; F and -NO2; and the re- maining of R72, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; - C(=O)NH2; -CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -O- CH2-CH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R72 is selected from the group consisting of hydrogen, F, Cl, Br and I; and the re- maining of R71, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; - C(=O)NH2; -CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R73 is selected from the group consisting of hydrogen, Cl; F; Br; I; -CN; -NO2; - C(=O)NH2; -CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; -NH2; and -NO2; or R74 is selected from the group consisting of hydrogen, F; -OH; -CN and -OCH3; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; -CN; -NO2; -OH; -SH; -C(=O)NH2; -CH(=N- OH); CH( N OCH3); C( O) O CH3; CH C(CN)2; OCH3; O CH2 CH3; CF3; me thyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl.
In a yet further specific embodiment, the present invention encompasses the use of compounds of formula I(A), wherein, X is CR4; Y is CR5; R1 is hydrogen; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2;
-CF2-CF3; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; R3 is selected from the group consisting of hydrogen, Cl; F; Br; I; -CN; -O-CH3; -C(CH3)2- OH; -CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)-O-CH3; -CF2- CF3; and the remaining of R4 and R5 independently of each other is selected from hydrogen; or R4 is hydrogen; and the remaining of R3 and R5 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; - C(CH3)2-OH; -CHF2; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3 and -CF2-CF3; or R5 is hydrogen; and the remaining of R3 and R4 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; - C(CH3)2-OH; -CHF2; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3 and -CF2-CF3. R71 is selected from the group consisting of hydrogen, -NH2; F and -NO2; and the re- maining of R72, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; - C(=O)NH2; -CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -O- CH2-CH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R72 is selected from the group consisting of hydrogen, F, Cl, Br and I; and the re- maining of R71, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; - C(=O)NH2; -CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R73 is selected from the group consisting of hydrogen, Cl; F; Br; I; -CN; -NO2; - C(=O)NH2; -CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; -NH2; and -NO2; or R74 is selected from the group consisting of hydrogen, F; -OH; -CN and -OCH3; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; -CN; -NO2; -OH; -SH; -C(=O)NH2; -CH(=N- OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; -CF3; me- thyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl.
In a further embodiment, the present invention encompasses the use of compounds of formula I(A), wherein, R1 is selected from the group consisting of hydrogen; -NH2; -CH2-OH; -CH2-OCH3; - CH2-O-(CH2)2-Si-(CH3)3; -C(=O)-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-O-phenyl; - C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4- CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH2-phenyl; -C(=O)-O-CH2-phenyl; -C(=O)- O-CH2-CH=CH; -C(=O)-OC(CH3)3; -CH2C(=O)-OCH3; -S(O)2-phenyl; -S(O)2-CF3; -S- phenyl and -C(=O)-NH2; wherein phenyl is substituted with F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2;
-CF2-CF3; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -C(=O)-O- (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; - C(=O)-O-C(CH3)3; R3 is selected from the group consisting of hydrogen, methyl, ethenyl, isopropenyl, ethynyl and cyclopropyl; and the remaining of R4 and R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; -CF3; -CHF2; -CH(F)-CF3; methyl, ethyl, pro- pyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl and tert butyl; or R4 is selected from the group consisting of hydrogen, F; Cl; Br and I; and the re- maining of R3 and R5 are independently of each other selected from the group con- sisting of methyl, ethenyl, isopropenyl, ethynyl, and cyclopropyl; R71 is selected from the group consisting of hydrogen, -NH2; F and -NO2; and the remain- ing of R72, R73 and R74 are independently of each other selected from the group con- sisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; - C(=O)NH2; -CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -O- CH2-CH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R72 is selected from the group consisting of hydrogen, F, Cl, Br and I; and the re- maining of R71, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; - C(=O)NH2; -CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R73 is selected from the group consisting of hydrogen, Cl; F; Br; I; -CN; -NO2; - C(=O)NH2; -CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; -NH2; and -NO2; or R74 is selected from the group consisting of hydrogen, F; -OH; -CN and -OCH3; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; -CN; -NO2; -OH; -SH; -C(=O)NH2; -CH(=N- OH); CH( N OCH3); C( O) O CH3; CH C(CN)2; OCH3; O CH2 CH3; CF3; me thyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl.
In a specific embodiment of the fourth embodiment, the present invention encompasses the use of compounds of formula I(A), selected from:
3-(2-chloro-3-thienyl)-1H-indole;
3-[2-(trifluoromethyl)-3-thienyl]-1H-indole;
5-fluoro-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole;
5-chloro-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole;
3-[2-(trifluoromethyl)-3-thienyl]indol-1-amine;
5,6-difluoro-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole;
4,5-difluoro-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole;
3-[2-(trifluoromethyl)-3-thienyl]-1H-indole-5-carbonitrile;
3-(2-chloro-3-thienyl)-1H-indole-5-carbonitrile;
1-acetyl-3-[2-(trifluoromethyl)-3-thienyl]indole-5-carbonitrile;
5-cyclopropyl-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole;
3-(2-methyl-3-thienyl)-1H-indole-5-carbonitrile;
(E)-N-methoxy-1-[3-[2-(trifluoromethyl)-3-thienyl]-1H-indol-5-yl]methanimine;
(5E)-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole-5-carbaldehyde oxime;
3-(2-methyl-3-thienyl)-1H-indole-5-carbonitrile;
3-[2-(trifluoromethyl)-3-thienyl]-1H-indole-5-carboxamide;
7-amino-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole-5-carbonitrile;
3-(2-bromo-3-thienyl)-1H-indole-5-carbonitrile;
5-nitro-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole;
3-(2-iodo-3-thienyl)-1H-indole-5-carbonitrile;
3-(2-ethynyl-3-thienyl)-1H-indole-5-carbonitrile;
3-[2-(trifluoromethyl)-3-thienyl]-1H-indole;
5-fluoro-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole;
1-acetyl-3-[2-(trifluoromethyl)-3-thienyl]indole-5-carbonitrile;
3-(2-cyano-3-thienyl)-1H-indole-5-carbonitrile;
(E)-N-methoxy-1-[3-[2-(trifluoromethyl)-3-thienyl]-1H-indol-5-yl]methanimine;
(5E)-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole-5-carbaldehyde oxime;
3-(2-methyl-3-thienyl)-1H-indole-5-carbonitrile;
3-(2-bromo-3-thienyl)-1H-indole-5-carbonitrile;
5-nitro-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole;
3-(2-methyl-3-thienyl)-1H-indole-5-carbonitrile;
6-fluoro-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole-5-carbonitrile;
3-(2-cyclopropyl-3-thienyl)-1H-indole-5-carbonitrile;
3-[2-(trifluoromethyl)-3-thienyl]-1H-indole-5-carbonitrile;
5-fluoro-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole;
5-chloro-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole;
(E)-1-[3-(1H-indol-3-yl)-2-thienyl]-N-methoxy-methanimine;
(Z)-1-[3-(1H-indol-3-yl)-2-thienyl]-N-methoxy-methanimine;
phenyl-[3-[2-(trifluoromethyl)-3-thienyl]indol-1-yl]methanone;
1-(methoxymethyl)-3-[2-(trifluoromethyl)-3-thienyl]indole; methyl 3 [2 (trifluoromethyl) 3 thienyl]indole 1 carboxylate;
1-[3-(2-chloro-3-thienyl)indol-1-yl]propan-1-one;
3-(2-bromo-3-thienyl)-1H-indole;
3-[2-(trifluoromethyl)-3-thienyl]indol-1-amine;
[3-[2-(trifluoromethyl)-3-thienyl]indol-1-yl]methanol;
3-(2-methoxy-3-thienyl)-1H-indole;
5,6-difluoro-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole;
5-(trifluoromethyl)-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole;
4,5-difluoro-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole;
3-[2-(trifluoromethyl)-3-thienyl]-1H-indol-4-ol;
4-methoxy-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole;
3-(2-chloro-3-thienyl)-5-methoxy-1H-indole;
3-[2-(trifluoromethyl)-3-thienyl]-1H-indole-5-carbonitrile;
3-(2-chloro-3-thienyl)-1H-indole-5-carbonitrile;
3-[3-(2-chloro-3-thienyl)-1H-indol-5-yl]-5-(trifluoromethyl)-1,2,4-oxadiazole; 1-acetyl-3-[2-(trifluoromethyl)-3-thienyl]indole-5-carbonitrile;
5-cyclopropyl-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole;
3-(2-methyl-3-thienyl)-1H-indole-5-carbonitrile;
(E)-N-methoxy-1-[3-[2-(trifluoromethyl)-3-thienyl]-1H-indol-5-yl]methanimine; (5E)-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole-5-carbaldehyde oxime;
7-amino-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole-5-carbonitrile;
3-(2-bromo-3-thienyl)-1H-indole-5-carbonitrile;
5-nitro-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole;
3-(2-iodo-3-thienyl)-1H-indole-5-carbonitrile;
3-[2-(1-hydroxy-1-methyl-ethyl)-3-thienyl]-1H-indole-5-carbonitrile;
3-(2-cyclopropyl-3-thienyl)-1H-indole-5-carbonitrile;
3-(2-isopropenyl-3-thienyl)-1H-indole-5-carbonitrile;
3-[2-(1,2,2,2-tetrafluoroethyl)-3-thienyl]-1H-indole-5-carbonitrile;
3-[2-(trifluoromethyl)-3-thienyl]-1H-indole-2-thiol;
3-(2-chloro-3-thienyl)-1H-indole-2-carbonitrile;
3-(2-chloro-3-thienyl)-1H-indole-2-thiol;
3-(1H-indol-3-yl)thiophene-2-carbonitrile;
4-(1H-indol-3-yl)thiophene-3-carbonitrile;
3-(2,5-dichloro-3-thienyl)-1H-indole;
tert-butyl 3-[2-(trifluoromethyl)-3-thienyl]indole-1-carboxylate;
tert-butyl 3-(2-chloro-3-thienyl)indole-1-carboxylate;
3-(2-methyl-3-thienyl)-1H-indole;
3-[2-(trifluoromethyl)-3-thienyl]-1H-indole-4-carbonitrile;
1-(benzenesulfonyl)-3-[2-(trifluoromethyl)-3-thienyl]indole;
trimethyl-[2-[[3-[2-(trifluoromethyl)-3-thienyl]indol-1-yl]methoxy]ethyl]silane; methyl 2-[3-[2-(trifluoromethyl)-3-thienyl]indol-1-yl]acetate;
phenyl 5-cyano-3-[2-(trifluoromethyl)-3-thienyl]indole-1-carboxylate;
benzyl 5-cyano-3-[2-(trifluoromethyl)-3-thienyl]indole-1-carboxylate;
allyl 5-cyano-3-[2-(trifluoromethyl)-3-thienyl]indole-1-carboxylate; 1 [(E) but 2 enoyl] 3 [2 (trifluoromethyl) 3 thienyl]indole 5 carbonitrile;
methyl 3-[2-(trifluoromethyl)-3-thienyl]-1H-indole-6-carboxylate;
2-[[3-(2-chloro-3-thienyl)-1H-indol-5-yl]methylene]propanedinitrile;
7-nitro-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole-5-carbonitrile;
3-(3-thienyl)-1H-indole-5-carbonitrile;
7-fluoro-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole-5-carbonitrile;
3-[2-(1-hydroxyethyl)-3-thienyl]-1H-indole-5-carbonitrile;
3-(2,5-diiodo-3-thienyl)-1H-indole-5-carbonitrile;
3-[2-(2,2,2-trifluoro-1-hydroxy-ethyl)-3-thienyl]-1H-indole-5-carbonitrile;
2-fluoro-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole-5-carbonitrile;
methyl 3-(5-cyano-1H-indol-3-yl)thiophene-2-carboxylate;
3-[2-(1,1,2,2,2-pentafluoroethyl)-3-thienyl]-1H-indole-5-carbonitrile;
3-(2-vinyl-3-thienyl)-1H-indole-5-carbonitrile;
5-ethynyl-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole;
3-(4-methyl-3-thienyl)-1H-indole-5-carbonitrile;
3-[4-(trifluoromethyl)-3-thienyl]-1H-indole-5-carbonitrile;
2-(trifluoromethyl)-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole-5-carbonitrile;
3-[2-(trifluoromethyl)-3-thienyl]-1H-indole-2,5-dicarbonitrile;
methyl 5-cyano-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole-2-carboxylate;
2-difluoromethyl-3-[2-(trifluoromethyl)3-thienyl]-1H-indole-5-carbonitrile;
ethyl 5-cyano-3-[2-(trifluoromethyl)-3-thienyl]-1H-indole-2-carboxylate;
3-[5-(trifluoromethyl)thiazol-4-yl]-1H-indole-5-carbonitrile;
4-(5-ethynyl-1H-indol-3-yl)-5-(trifluoromethyl)thiazole;
3-[5-(trifluoromethyl)isothiazol-4-yl]-1H-indole-5-carbonitrile;
3-[3-(trifluoromethyl)isothiazol-4-yl]-1H-indole-5-carbonitrile.
3-(2-chloro-3-thirnyl)-1H-indole-4-carbonitrile
1-[3-[2-(trifluoromethyl)-3-thienyl]indol-1-yl]ethanone
3-[2,5-bis(trifluoromethyl)-3-thienyl]-1H-indole-5-carbonitrile. In an embodiment, the present invention provides a use of an heteroaryl compound of formula (I),
Figure imgf000054_0001
formula (I)
wherein,
X denotes N;
Y denotes CR5 or N;
A together with the two carbon atoms of pyrrole ring, is selected from the group consist- ing of an unsubstituted or substituted 6-membered aryl; R1 is selected from the group consisting of hydrogen; -(CH2)aOR6; -(CH2)bC(=O)-R7; - C(=O)-(CH2)c-R8; -C(=O)-(CH2)d-OR9; -C(=O)-CR10(=CR11); -C(=O)-(CH2)e-SR12; - (CH2)f O C( O) R ; (CH2)g C( O) OR ; C( O) O (CH2)h R ; O C( O) O (CH2)i R16; -C(=O)-NR17R18; -C(=S)-NR19R20; -NR21R22; -S(=O)j-R23; -(CH2)k-Si-(R24)l and - (CH2)m-O-(CH2)n-Si-(R25)0; -(CX2)bC(=O)-R25’; C(=O)-(CX2)c-R25’’; -(CHX)bC(=O)-R25’’’ C(=O)-(CHX)c-R25’’’’; wherein X is selected from group consisting of F, Cl, Br and I; R2 is selected from the group consisting of hydrogen; halogen; CN; -C(=O)-OR14; unsub- stituted or substituted alkyl; unsubstituted or substituted cycloalkyl and unsubstituted or substituted cycloalkenyl;
R3 is selected from the group consisting of halogen; CN; -OR6, -C(=O)-OR14, SF5, -C(=O) R7, -C(=O)CF3, -C(=O)CHF2; unsubstituted or substituted alkyl; unsubstituted or sub- stituted heteroalkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloal- kenyl; unsubstituted or substituted heterocycloalkyl; and unsubstituted or substituted heterocycloalkenyl;
R5 is selected from the group consisting of hydrogen; halogen; CN; unsubstituted or sub- stituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted al- kynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloal- kenyl; unsubstituted or substituted heterocycloalkyl and unsubstituted or substituted heterocycloalkenyl;
R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24 and R25, R25’, R25’’, R25’’’, R25’’’’ are independently of each other, selected from the group con- sisting of hydrogen; halogen; hydroxy, CN; unsubstituted or substituted alkyl; unsub- stituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or sub- stituted aryl; unsubstituted or substituted -(alkylene)-aryl; unsubstituted or substituted heterocycloalkyl; unsubstituted or substituted heterocycloalkenyl; unsubstituted or substituted heteroaryl;
or R17 together with R18 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substituted;
or R19 together with R20 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein,
the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
or R21 together with R22 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein,
the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
a is 0, 1, 2 or 3; b is 0, 1, 2 or 3; c is 0, 1, 2 or 3; d is 0, 1, 2 or 3; e is 0, 1, 2 or 3; f is 0, 1, 2 or 3; g is 0, 1, 2 or 3; h is 1, 2 or 3; i is 1, 2 or 3; j is 0, 1, 2 or 3; k is 0, 1, 2 or 3; l is 0, 1, 2 or 3; m is 0, 1, 2 or 3; n is 0, 1, 2 or 3; o is 1, 2 or 3;
or each compound in the form of a stereoisomer, an agriculturally acceptable salt, a pro- drug, a tautomer, an isotopic form, a N oxide, a S oxide or a mixture thereof, as an agricultural fungicide. In another embodiment, the present invention provides the use of a compound of formula (I), wherein,
A together with the two carbon atoms of pyrrole ring, is
Figure imgf000056_0001
wherein,
R71, R72, R73, R74, are independently of each other, selected from the group consisting of H; halogen; CN; -NO2; -NH2; -OH; -SH; oxo; -C(=O)-OR14; -C(=O)-NR17R18; -C(=S)- NR19R20; -N-CN; -S-CN; -O-CN, -CR115(=N-OR116); unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubsti- tuted or substituted heteroalkyl, heteroalkenyl or heteroalkynyl; unsubstituted or sub- stituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substi- tuted heterocycloalkyl, unsubstituted or substituted aryl; unsubstituted or substituted heteroaryl and unsubstituted or substituted heterocycloalkenyl;
R115 and R116 are independently of each other selected from the group consisting of H; hal- ogen; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsub- stituted or substituted alkynyl; unsubstituted or unsubstituted or substituted cycloal- kyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substituted heterocy- cloalkyl; and unsubstituted or substituted heterocycloalkenyl;
and whereby,
the alkyl are straight-chain or branched, and comprise 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms as chain links;
the alkenyl are straight-chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
the alkynyl are straight-chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
the heteroalkyl, heteroalkenyl and heteroalkynyl comprise 1, 2, 3, 4, 5 or 6 carbon atoms and 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from O, N(H) or S as chain links;
the alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl and heteroalkynyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -OH, -SH, -NH2, -NH(C1-C6)alkyl,-NH-CH(CH3)2, -N(C1-C6-alkyl)2, -N(C1-C6-alkyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, - C(=O)-O-phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -CH2-C(=O)-O-C1-C6-alkyl, - C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -NH-C(=O)C(CH3)3, -S(=O)-C1-C6- alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -NH-SO2-phenyl, - N(CH3)-SO2-phenyl, -C1-C6-alkyl, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phenyl)3, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, oxetanyl, piperidinyl, piperazinyl, mor- pholinyl, thiomorpholinyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, oxadiazolyl, thiadi azolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; wherein, the alkyl, heterocycloalkyl, cycloalkyl, aryl or heteroaryl are themselves unsubstituted or substi- tuted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl;
the cycloalkyl and cycloalkenyl comprises 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms as ring members;
the heterocycloalkyl and heterocycloalkenyl are 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from the group consisting of O, N(H) and S as ring members;
the cycloalkyl, cycloalkenyl, heterocycloalkyl or heterocycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -C(=O)-H, - C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phenyl, -C(=O)-NH2, - C(=O)-NH(C1-C6)alkyl, -NH-C(=O)C(CH3)3, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2- NH2, -C1-C6-alkyl, -CF3, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, furyl, oxazolyl, thi- azolyl, pyrazolyl, thiophenyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, py- razinyl, phenyl and -CH2-phenyl; wherein the alkyl, cycloalkyl, heterocycloalkyl, aryl or het- eroaryl, are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of F, Cl, Br, I, -CN, -NH2, -CF3, -OH, -SH, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, -OCH3, -O-C2H5, phenyl and -CH2-phenyl;
the aryl are mono-, bicyclic or tricyclic and comprise 6, 10 or 14 carbon atoms;
the heteroaryl are mono- or bicyclic and 5- or 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently selected from the group consisting of O, N(H) or S as ring members;
the aryl or heteroaryl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -OH, -SH, -O-CH3, -O-C2H5, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -N(C1-C6-alkyl)2, -N(C1-C6-al- kyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O- phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, - C(=O)-NH-phenyl, -S(=O)-C1-C6-alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -NH-SO2-phenyl, -N(CH3)-SO2-phenyl, -C1-C6-alkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, 1, 2, 4-oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; wherein the alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl. In yet another embodiment, the present invention provides the use of a compound of formula (I), wherein,
X denotes N and Y denotes CR5; or X denotes N and Y denotes N;
A together with the two carbon atoms of pyrrole ring, is
Figure imgf000058_0001
R1 is selected from the group consisting of hydrogen; -CH2-OH; -CH2-OCH3; -CH2-O- CH(CH3)2; -CH2-O-(CH2)2-Si(CH3)3; -C(=O)-CH3; -C(=O)-CH2-CH3; -(C=O)-(CH2)2- CH3; -(C=O)-(CH2)3-CH3; -(C=O)-(CH2)3-CH3; -(C=O)-(CH2)4-CH3; -(C=O)-(CH2)5- CH3; -C(=O)-C(CH3)3; -C(=O)-CH2-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-cyclopropyl; - C(=O)-phenyl; -C(=O)-CH2-cyclopropyl; -C(=O)-CH2-phenyl; -CH2-O-(C=O)-CH3; - CH2-O-(C=O)-CH2-CH3; -CH2-O-(C=O)-(CH2)2-CH3; -CH2-O-(C=O)-(CH2)3-CH3; - CH2-O-(C=O)-(CH2)4-CH3; -CH2-O-(C=O)-(CH2)5-CH3; -CH2-O-(C=O)-C(CH3)3; -CH2- O-(C=O)-phenyl; -C(=O)-OCH3; -C(=O)-OCH2-CH3; -CHF-C(=O)-OCH3; -CHF- C(=O)-OCF3; -CHF-C(=O)-OCH2-CH3; -CHF-C(=O)-OC(CH3)3; -CHF-C(=O)- OCH(CH3)2; -CF2-C(=O)-OCH3; -CF2-C(=O)-OCH2-CH3; -CF2-C(=O)-OC(CH3)3; -CF2- C(=O)-OCH(CH3)2; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4- CH3; -C(=O)-O-(CH2)5-CH3;-C(=O)-O-CH2-CH(CH3)2; -C(=O)-O-CH(CH3)2; -C(=O)-O- CH2-CCl3; -C(=O)-O-C(CH3)3; -C(=O)-O-(CH2)6-CH3; -C(=O)-O-CH2-CH=CH; -C(=O)- O-CH2-C≡CH; -C(=O)O-phenyl; -C(=O)-O-CH2-phenyl; -CH2-C(=O)-OCH3; -CH2- C(=O)-OCH2-CH3; -CH2-C(=O)-O(CH2)2-CH3; -CH2-C(=O)-O(CH2)3-CH3; -CH2-C(=O)- O(CH2)4-CH3; -CH2-C(=O)-O(CH2)5-CH3; -CH2-C(=O)-OC(CH3)3; -CH2-C(=O)-O-CH2- CH=CH; -CH2-C(=O)-O-CH=CH-CH3; -C(=O)-NH2; -C(=O)-NH-CH3; -C(=O)-N- (CH3 ) 2; -C(=O)-pyridyl; -C(=O)-pyrimidinyl; -C(=S)-NH2; -C(=S)-NH-CH3; -C(=S)-N- (CH3 ) 2; -C(=S)-pyridyl; -C(=S)-pyrimidinyl; -S(=O)2-CH3; -S(=O)2-CH2-CH3; -S(=O)2- (CH2)2-CH3; -S(=O)2-(CH2)2-CH3; -S(=O)2-tert butyl; -S(=O)2-phenyl; wherein, cyclo- propyl, phenyl, pyridyl and pyrimidinyl is unsubstituted or substituted with 1, 2 or 3, substituents independently of each other selected from the group consisting of F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -C(=O)-O-CH3; - C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4- CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; methyl, ethyl, propyl, butyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl, tert butyl, cyclopropyl, cyclo- butyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohex- enyl; wherein alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN, - OH, -SH, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -N(C1-C6-alkyl)2, -N(C1-C6-alkyl)-phe- nyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phe- nyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -CH2-C(=O)-O-C1-C6-alkyl, -C(=O)- NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -NH-C(=O)-C(CH3)3, -S(=O)-C1-C6- alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -NH-SO2- phenyl, -N(CH3)-SO2-phenyl, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phenyl)3, phenyl and CH2 phenyl; wherein, the cycloalkyl or cycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O- C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)- OCH3, -NH-C(=O)-CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R3 is selected from the group consisting of Cl; F; Br; I; CN; -OCH3; -C(=O)-O-CH3; - C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4- CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; SF5, -C(=O)CH3, -C(=O)CF3, -C(=O)CHF2, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, ethynyl, propynyl, butynyl, cyclo- propyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopen- tenyl, cyclohexenyl, oxetanyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, 1,2,4-oxadiazolyl, 1,3,4-trimethyl piperazinyl, 2,3-dihydrofuranyl, 2,3-dihydrothienyl, 2,3-dihydropyrrolyl, 2,3-dihydroisoxazolyl, 1,4-dihydropyridin-1-yl, dihydropyranyl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihy- drooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl and 3,4-dihydrooxazol- 4-yl; wherein, alkyl, alkenyl and alkynyl are independently of each other unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN; -OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -NO2; -NH2; -NH(CH3)2; wherein, the cycloalkyl, cycloalkenyl, heterocycloalkyl and heterocycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, - CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, - C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH-C(=O)-CH3, -NH-C(=O)- C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2- phenyl; R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; methyl, ethyl, pro- pyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, tetrahydro- furanyl, tetrahydrothiophenyl, tetrahydropyranyl, oxetanyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, 1,2,4-oxadiazolyl, 1,3,4-trimethyl piperazinyl, 2,3-dihy- drofuranyl, 2,3-dihydrothienyl, 2,3-dihydropyrrolyl, 2,3-dihydroisoxazolyl, 1,4-dihydro- pyridin-1-yl, dihydropyranyl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihy- drooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl and 3,4-dihydrooxazol-4-yl; wherein, alkyl and alkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2; -CF2-CF3; -C(=O)-O-CH3; -C(=O)-O- CH2-CH3; -NO2; -NH2 and -NH(CH3)2; and wherein, the cycloalkyl, cycloalkenyl, het- erocycloalkyl and heterocycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R , R , R , R are independently of each other, selected from the group consisting of H;
Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; oxo; -C(=O)NH2; -CH(=N- OH); -CH(=N-OCH3); -CH(=N-OCH2CH3); -CH(=N-O(CH2)2CH3); -CH(=N- O(CH2)4CH3); ; -N-CN; -S-CN; -O-CN; -C(CH3)(=N-OH); -C(CH3)(=N-OCH3); -C(=O)- O-CH3; -CH=C(CN)2; -O-CH3; -O-CH2-CH3; -O(CH2)2CH3; -O(CH2)3CH3; - O(CH2)4CH3; -O(CH2)5CH3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; iso- pentyl; tert butyl; ethenyl; 1-propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; bu- tynyl; cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cyclopropenyl; cyclobutenyl; cy- clopentenyl; cyclohexenyl; oxetanyl; piperidinyl; piperazinyl; morpholinyl; thiomor- pholinyl; 1,2,4-oxadiazolyl; 1,3,4-trimethyl piperazinyl; 2,3-dihydrofuranyl; 2,3-dihy- drothienyl; 2,3-dihydropyrrolyl; 2,3-dihydroisoxazolyl and 2,3-dihydrooxazol-2-yl; and wherein, alkyl, alkenyl and alkynyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of F, Cl, -CN, -OH, -NH2, -C(=O)-OH, -C(=O)-OCH3, -Si-(CH3)3, -Si-(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phenyl)3, phenyl and - CH2-phenyl; and wherein, the cycloalkyl, cycloalkenyl, heterocycloalkyl and heterocy- cloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other, selected from the group consisting of 1, 2, 3, 4 or 5 substit- uents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH-C(=O)-CH3, -NH-C(=O)- C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2- phenyl. In an embodiment, the present invention provides the use of a compound of formula (I), wherein the compound of formula (I) is a compound of formula I(A),
formula I(A)
Figure imgf000060_0001
X denotes N and Y denotes CR5; or
X denotes N and Y denotes N;
or each compound in the form of a stereoisomer, an agriculturally acceptable salt, a prodrug, a tautomer, an isotopic form, a N-oxide or a S-oxide thereof, as an agricultural fungicide. In an embodiment, the present invention provides the use of a compound of formula I(A), wherein, R1 is selected from the group consisting of hydrogen; -CH2-OH; -CH2-OCH3; -CH2-O- CH(CH3)2; -CH2-O-(CH2)2-Si(CH3)3; -C(=O)-CH3; -C(=O)-CH2-CH3; -C(=O)-(CH2)2- CH3; -C(=O)-(CH2)3-CH3; -C(=O)-(CH2)4-CH3; -C(=O)-(CH2)5-CH3;-C(=O)-C(CH3)3; - C(=O)-CH2-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-phenyl; -C(=O)-cyclopropyl; -C(=O)- CH2-cyclopropyl; -C(=O)-CH2-phenyl; -CH2-O-(C=O)-CH3; -CH2-O-(C=O)-CH2-CH3; - CH2-O-(C=O)-(CH2)3-CH3; -CH2-O-(C=O)-(CH2)4-CH3; -CH2-O-(C=O)-(CH2)5-CH3 ; - CH2-O-(C=O)-C(CH3)3; -CH2-O-(C=O)-phenyl; -C(=O)-OCH3; C(=O)-O-(CH2)2CH3; - C( O) O (CH2)3 CH3; C( O) O (CH2)4 CH3; C( O) O (CH2)5 CH3; C( O) OCH2 CH(CH3)2; -C(=O)-OCH(CH3)2; -C(=O)-O-CH2-CCl3; -C(=O)-OC(CH3)3; -C(=O)-O- (CH2)6-CH3; -C(=O)-O-CH2-CH=CH; -C(=O)-O-CH2-C≡CH; -C(=O)O-phenyl; -C(=O)- O-CH2-phenyl; -CH2-C(=O)-OCH3; -CH2-C(=O)-OCH2-CH3; -CH2-C(=O)-O(CH2)2- CH3; -CH2-C(=O)-O(CH2)3-CH3; -CH2-C(=O)-O(CH2)4-CH3; -CH2-C(=O)-O(CH2)5-CH3; -CH2-C(=O)-OC(CH3)3; -CH2-C(=O)-O-CH2-CH=CH; -CH2-C(=O)-O-CH=CH-CH3; - C(=O)-NH2; -C(=O)-NH-CH3; -C(=O)-N-(CH3 ) 2; -C(=O)-pyridyl; -C(=O)-pyrimidinyl; - C(=S)-NH2; -C(=S)-NH-CH3; -C(=S)-N-(CH3)2; -C(=S)-pyridyl; -C(=S)-pyrimidinyl; - S(=O)2-CH3; -S(=O)2-CH2-CH3; -S(=O)2-(CH2)2-CH3; -S(=O)2-(CH2)2-CH3; -S(=O)2- tertbutyl; -S(=O)2-phenyl; -CHF-C(=O)-OCH3; -CHF-C(=O)-OCF3; -CHF-C(=O)- OCH2-CH3; -CHF-C(=O)-OC(CH3)3; -CHF-C(=O)-OCH(CH3)2; -CF2-C(=O)-OCH3; - CF2-C(=O)-OCH2-CH3; -CF2-C(=O)-OC(CH3)3; -CF2-C(=O)-OCH(CH3)2; wherein, cy- clopropyl, phenyl, pyridyl and pyrimidinyl is unsubstituted or substituted with 1, 2 or 3, substituents independently of each other selected from the group consisting of F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -C(=O)-O-CH3; - C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5- CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; methyl, ethyl, propyl, butyl, hexyl, hep- tyl, isopropyl, isobutyl, isopentyl, tert butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclo- hexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl; wherein alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, F, Br, I, CN, -OH, -SH, -NH2, -NH(C1- C6)alkyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O- phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-O-C1-C6-alkyl, -C(=O)-NH2, -C(=O)-NH(C1- C6)alkyl, -C(=O)-NH-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -CF3, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phenyl)3, phenyl and -CH2-phenyl; wherein, the cycloalkyl or cycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, -CH2- C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH-C(=O)-CH3, -NH- C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R3 is selected from the group consisting of Cl; F; Br; I; CN; -O-CH3; -O-CH2-CH3; -C(=O)- O-CH3; -C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O- (CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; SF5, - C(=O)CH3, -C(=O)CF3, -C(=O)CHF2, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, ethynyl, propynyl, bu- tynyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cy- clopentenyl and cyclohexenyl; wherein, alkyl, alkenyl or alkynyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -NO2; - NH2; -NH(CH3)2; wherein, the cycloalkyl and cycloalkenyl are unsubstituted or substi- tuted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, CN, OH, NH2, O CF3, SH, O CH3, O C2H5, C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH- C(=O)-CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; methyl, ethyl, pro- pyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl; wherein, alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of Cl, Br, F, I, CN; -CF3; - CCl3; -CHF2; -CF2-CF3; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -NO2; -NH2; -NH(CH3)2; and wherein, the cycloalkyl and cycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consist- ing of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R71, R72, R73 and R74 are independently of each other, selected from the group consisting of H; Cl; F; Br; I; -CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; -C(=O)NH2; -CH(=N- OH); -CH(=N-OCH3); -CH(=N-OCH2CH3); -CH(=N-O(CH2)2CH3); -CH(=N- O(CH2)4CH3); -C(CH3)(=N-OH); -C(CH3)(=N-OCH3); -C(=O)-O-CH3; -C(=O)-O- (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; - C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1-propenyl; isopropenyl; isobu- tenyl; ethynyl; propynyl; butynyl; cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cy- clopropenyl; cyclobutenyl; cyclopentenyl; cyclohexenyl; oxetanyl; piperidinyl; piper- azinyl; morpholinyl; thiomorpholinyl; 1,2,4-oxadiazolyl; 1,3,4-trimethyl piperazinyl; 2,3-dihydrofuranyl; 2,3-dihydrothienyl; 2,3-dihydropyrrolyl; 2,3-dihydroisoxazolyl and 2,3-dihydrooxazol-2-yl; and wherein, alkyl, alkenyl and alkynyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of F, Cl, -CN, -OH, -NH2, -C(=O)-OH, -C(=O)-OCH3, -Si-(CH3)3, -Si-(C2H5)3, -Si-(CH3)2-phe- nyl, -Si-(phenyl)3, phenyl and -CH2-phenyl; and wherein, the cycloalkyl, cycloalkenyl, heterocycloalkyl and heterocycloalkenyl are independently of each other unsubsti- tuted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, - CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH-C(=O)-CH3, - NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl. In another embodiment, the present invention provides the use of a compound of formula I(A), wherein, R1 is selected from the group consisting of hydrogen; -NH2; -CH2-OH; -CH2-OCH3; -CH2- O-(CH2)2-Si-(CH3)3; -C(=O)-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-O-phenyl; -CHF- C(=O)-OCH3; -CHF-C(=O)-OCF3; -CHF-C(=O)-OCH2-CH3; -CHF-C(=O)-OC(CH3)3; - CHF-C(=O)-OCH(CH3)2; -CF2-C(=O)-OCH3; -CF2-C(=O)-OCH2-CH3; -CF2-C(=O)- OC(CH3)3; CF2 C( O) OCH(CH3)2; C( O) O CH2 CH3; C( O) O (CH2)2 CH3; C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH2- phenyl; -C(=O)-O-CH2-phenyl; -C(=O)-O-CH2-CH=CH; -C(=O)-OC(CH3)3; - CH2C(=O)-OCH3; -S(O)2-phenyl; -S(O)2-CF3; -S-phenyl and -C(=O)-NH2; wherein phenyl is substituted with F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2;
-CF2-CF3; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -C(=O)-O- (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; - C(=O)-O-C(CH3)3; R3 is selected from the group consisting of Cl; F; Br; I; -CN; -O-CH3; -O-CH2-CH3; - C(CH3)2-OH; -CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O- CH(CH3)2; -C(=O)-O-C(CH3)3; SF5, -C(=O)CH3, -C(=O)CF3, -C(=O)CHF2, -CF2-CF3; methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopen- tyl and cyclohexyl; and the R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; -CF3; -CHF2; -CH(F)-CF3; methyl, ethyl, propyl, butyl, pentyl, hexyl, hep- tyl, isopropyl, isobutyl, isopentyl and tert butyl; or R5 is selected from the group consisting of hydrogen, F; Cl; Br; I; CN; -CF3; -CHF2;
-CH(F)-CF3; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, iso- pentyl and tert butyl; and the R3 is selected from the group consisting of Cl; F; Br; I; CN; -CF3; -O-CH3; -O-CH2-CH3; -C(CH3)2-OH; -CHF2; -CH(F)-CF3; -CH(CH3)2-OH; - CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)- O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CF2-CF3; methyl, ethyl, pro- pyl, butyl, isopropyl, isobutyl, tert butyl, ethenyl, propenyl, butenyl, isopropenyl, iso- butenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclo- hexyl; R71 is selected from the group consisting of hydrogen, -NH2; F ; -NH-CH3; -N(CH3)2 and - NO2; and the remaining of R72, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; - N(CH3)2; -OH; -SH; -C(=O)NH2; -CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); - C(CH3)(=N-OCH3); -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; - C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; - O-CH2-CH3; -CF3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1-propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclo- propyl; and 1,2,4-oxadiazolyl; or R72 is selected from the group consisting of hydrogen, F, Cl, Br and I; and the remain- ing of R71, R73 and R74 are independently of each other selected from the group con- sisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; - C(=O)NH2; -CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); -C(CH3)(=N-OCH3); - C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; - C( O) O CH(CH3)2; C( O) O C(CH3)3; CH C(CN)2; OCH3; O CH2 CH3; CF3; me thyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1- propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; and 1,2,4- oxadiazolyl; or R73 is selected from the group consisting of hydrogen, Cl; F; Br; I; -CN; -NO2; -NH2; - NH-CH3; -N(CH3)2; -C(=O)NH2; -CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); - C(CH3)(=N-OCH3); -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; - C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; - O-CH2-CH3; -CF3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1-propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclo- propyl; and 1,2,4-oxadiazolyl; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; -NH2; -NH-CH3; - N(CH3)2; and -NO2; or R74 is selected from the group consisting of hydrogen, F; -OH; -CN and -OCH3; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; -CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; -C(=O)NH2; -CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); -C(CH3)(=N-OCH3); -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; - C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; -CF3; me- thyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1- propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; and 1,2,4- oxadiazolyl.
In yet another embodiment, the present invention provides the use of a compound of formula I(A), , wherein the compound is: 3-[5-(trifluoromethyl)isothiazol-4-yl]-1H-indole-5-carbonitrile; 3-[3- (trifluoromethyl)isothiazol-4-yl]-1H-indole-5-carbonitrile; 3-(3,5-dimethylisothiazol-4-yl)-1H-in- dole-5-carbonitrile; and 3-(5-methylthiadiazol-4-yl)-1H-indole-5-carbonitrile. In another embodiment, the present invention provides the use of a compound of formua (I), wherein,
X is N; Y is CR5 or N
A is
Figure imgf000064_0001
R1 is hydrogen; R2 is hydrogen; R3 is selected from the group consisting of Cl; F; Br; I; -CN; -O-CH3; -C(CH3)2-OH; -CH(CH3)- OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)-O-CH3; -CF2-CF3; methyl, ethenyl, iso- propenyl, ethynyl and cyclopropyl; and the R5 is selected from hydrogen; or R is hydrogen; and the R is selected from the group consisting of Cl; F; Br; I; CN; CF3; -O-CH3; -O-CH2-CH3; -C(CH3)2-OH; -CHF2; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O- CH3; -C(=O)-O-C(CH3)3; -CF2-CF3; methyl, tert butyl, ethenyl, isopropenyl, ethynyl and cyclopropyl; R71, R72, R73 and R74 are independently of each other, selected from the group consisting of H; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; oxo; -C(=O)NH2; -CH(=N-OH); - CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -O-CH3; -O(CH2)5CH3; -CF3; methyl; ethynyl; propynyl; butynyl; cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cyclopropenyl; cyclobutenyl; cyclopentenyl; cyclohexenyl; oxetanyl; piperidinyl; piperazinyl; morpholinyl; thiomorpholinyl; 1,2,4-oxadiazolyl. In another embodiment, the present invention provides the use of compound of formula (I), , wherein,
X is N; Y is CH or N
A is:
Figure imgf000065_0001
R1 is hydrogen; R2 is hydrogen; R3 is -CF3;
R71, R72, R73 and R74 are independently of each other, selected from the group consisting of hy- drogen; Cl; F; Br; I; CN; methyl, ethynyl and propynyl. In another embodiment, the present invention provides the use of compound of formula (I), wherein,
X is N; Y is CH or N
A is:
Figure imgf000065_0002
R1 is hydrogen; R2 is hydrogen; R3 is -CHF2 or CH2F;
R71, R72, R73 and R74 are independently of each other, selected from the group consisting of hy- drogen; Cl; F; Br; I; CN; methyl, ethynyl and propynyl. In an embodiment, the present invention provides a heteroaryl compound of formula (I),
Figure imgf000066_0001
formula (I)
wherein,
X denotes N; Y denotes CR5 or N;
A together with the two carbon atoms of pyrrole ring, is
Figure imgf000066_0002
R1 is selected from the group consisting of hydrogen; -(CH2)aOR6; -(CH2)bC(=O)-R7; - C(=O)-(CH2)c-R8; -C(=O)-(CH2)d-OR9; -C(=O)-CR10(=CR11); -C(=O)-(CH2)e-SR12; - (CH2)f-O-C(=O)-R13; -(CH2)g-C(=O)-OR14; -C(=O)-O-(CH2)h-R15; -O-C(=O)-O-(CH2)i- R16; -C(=O)-NR17R18; -C(=S)-NR19R20; -NR21R22; -S(=O)j-R23; -(CH2)k-Si-(R24)l and - (CH2)m-O-(CH2)n-Si-(R25)0; -(CX2)bC(=O)-R25’; C(=O)-(CX2)c-R25’’; -(CHX)bC(=O)-R25’’’ C(=O)-(CHX)c-R25’’’’; wherein X is selected from group consisting of F, Cl, Br and I; R2 is selected from the group consisting of hydrogen; halogen; CN; -C(=O)-OR14; unsub- stituted or substituted alkyl; unsubstituted or substituted cycloalkyl and unsubstituted or substituted cycloalkenyl;
R3 is selected from the group consisting of halogen; CN; -OR6, -C(=O)-OR14, SF5, -C(=O) R7, -C(=O)CF3, -C(=O)CHF2; unsubstituted or substituted alkyl; unsubstituted or sub- stituted heteroalkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloal- kenyl; unsubstituted or substituted heterocycloalkyl; and unsubstituted or substituted heterocycloalkenyl;
R5 is selected from the group consisting of hydrogen; halogen; CN; unsubstituted or sub- stituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted al- kynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloal- kenyl; unsubstituted or substituted heterocycloalkyl and unsubstituted or substituted heterocycloalkenyl;
R6, R7, R8, R9, R10, R11, R12, R13, R15, R16, R17, R18, R19, R20, R21, R22, R23, R25, R25’, R25’’, R25’’’ and R25’’’’ are independently of each other, selected from the group consisting of hy- drogen; halogen; hydroxy, CN; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substituted aryl; unsubstituted or substituted -(alkylene)-aryl; unsubstituted or substituted heterocyclo- alkyl; unsubstituted or substituted heterocycloalkenyl; unsubstituted or substituted heteroaryl; R is selected from the group consisting of halogen; CN; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; un- substituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsub- stituted or substituted aryl; unsubstituted or substituted -(alkylene)-aryl; unsubstituted or substituted heterocycloalkyl; unsubstituted or substituted heterocycloalkenyl; un- substituted or substituted heteroaryl;
or R17 together with R18 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substituted;
or R19 together with R20 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein,
the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
or R21 together with R22 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substituted;
R71, R72, R73 and R74 are independently of each other, selected from the group consisting of H; halogen; CN; -NO2; -NH2; -OH; -SH; oxo; -(CH2)g-C(=O)-OR14; -C(=O)-NR17R18; - C(=S)-NR19R20; -N-CN; -S-CN; -O-CN, -CR115(=N-OR116); unsubstituted or substi- tuted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or substituted heteroalkyl, heteroalkenyl or heteroalkynyl; unsubsti- tuted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubsti- tuted or substituted heterocycloalkyl and unsubstituted or substituted heterocycloal- kenyl;
R115 and R116 are independently of each other selected from the group consisting of H; halo- gen; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubsti- tuted or substituted alkynyl; unsubstituted or unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substituted heterocycloal- kyl; and unsubstituted or substituted heterocycloalkenyl;
and whereby,
if not specified otherwise, the alkyl are straight-chain or branched, and comprise 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms as chain links;
the alkenyl are straight-chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
the alkynyl are straight-chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
the heteroalkyl, heteroalkenyl and heteroalkynyl comprise 1, 2, 3, 4, 5 or 6 carbon atoms and 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from O, N(H) or S as chain links;
if not specified otherwise, the alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl and heteroal- kynyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -OH, -SH, -NH2, -NH(C1-C6)alkyl, -NH- CH(CH3)2, -N(C1-C6-alkyl)2, -N(C1-C6-alkyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)- OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, - CH2 C( O) O C1 C6 alkyl, C( O) NH2, C( O) NH(C1 C6)alkyl, C( O) NH phenyl, NH C(=O)C(CH3)3, -S(=O)-C1-C6-alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, - S(=O)2-NH2, -NH-SO2-phenyl, -N(CH3)-SO2-phenyl, -C1-C6-alkyl, -Si-(CH3)3, -Si(C2H5)3, -Si- (CH3)2-phenyl, -Si-(phenyl)3, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, oxetanyl, pi- peridinyl, piperazinyl, thiomorpholinyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, oxadi- azolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; wherein, the alkyl, heterocycloalkyl, cycloalkyl, aryl or heteroaryl are themselves unsubsti- tuted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O- C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; the cycloalkyl and cycloalkenyl comprises 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms as ring members;
the heterocycloalkyl and heterocycloalkenyl are 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from the group consisting of O, N(H) and S as ring members;
the cycloalkyl, cycloalkenyl, heterocycloalkyl or heterocycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -C(=O)-H, - C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phenyl, -C(=O)-NH2, - C(=O)-NH(C1-C6)alkyl, -NH-C(=O)C(CH3)3, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2- NH2, -C1-C6-alkyl, -CF3, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, furyl, oxazolyl, thi- azolyl, pyrazolyl, thiophenyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, py- razinyl, phenyl and -CH2-phenyl; wherein the alkyl, cycloalkyl, heterocycloalkyl, aryl or het- eroaryl, are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of F, Cl, Br, I, -CN, -NH2, -CF3, -OH, -SH, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, -OCH3, -O-C2H5, phenyl and -CH2-phenyl;
the aryl are mono-, bicyclic or tricyclic and comprise 6, 10 or 14 carbon atoms;
the heteroaryl are mono- or bicyclic and 5- or 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently selected from the group consisting of O, N(H) or S as ring members;
the aryl or heteroaryl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -OH, -SH, -O-CH3, -O-C2H5, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -N(C1-C6-alkyl)2, -N(C1-C6-al- kyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O- phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, - C(=O)-NH-phenyl, -S(=O)-C1-C6-alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -NH-SO2-phenyl, -N(CH3)-SO2-phenyl, -C1-C6-alkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, 1, 2, 4-oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; wherein the alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl a is 0, 1, 2 or 3; b is 0, 1, 2 or 3; c is 0, 1, 2 or 3; d is 0, 1, 2 or 3; e is 0, 1, 2 or 3; f is 0, 1, 2 or 3; g is 0, 1, 2 or 3; h is 1, 2 or 3; I is 1, 2 or 3; j is 0, 1, 2 or 3; k is 0, 1, 2 or 3; l is 0, 1, 2 or 3; m is 0, 1, 2 or 3; n is 0, 1, 2 or 3; o is 1, 2 or 3; or each compound in the form of a stereoisomer, an agriculturally acceptable salt, a prodrug, a tautomer, an isotopic form, a N-oxide, a S-oxide or a mixture thereof. In another embodiment, the present invention provides a compound of formula (I), wherein, X denotes N and Y denotes CR5; or
X denotes N and Y denotes N;
A together with the two carbon atoms of pyrrole ring, is
Figure imgf000069_0001
R1 is selected from the group consisting of hydrogen; -CH2-OH; -CH2-OCH3; -CH2-O- CH(CH3)2; -CH2-O-(CH2)2-Si(CH3)3; -C(=O)-CH3; -C(=O)-CH2-CH3; -(C=O)-(CH2)2- CH3; -(C=O)-(CH2)3-CH3; -(C=O)-(CH2)3-CH3; -(C=O)-(CH2)4-CH3; -(C=O)-(CH2)5- CH3; -C(=O)-C(CH3)3; -C(=O)-CH2-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-cyclopropyl; - C(=O)-phenyl; -C(=O)-CH2-CH3; -C(=O)-(CH2)2-CH3; -C(=O)-(CH2)3-CH3; -C(=O)- (CH2)4-CH3; -C(=O)-(CH2)5-CH3; -C(=O)-CH2-cyclopropyl; -C(=O)-CH2-phenyl; -CH2- O-(C=O)-CH3; -CH2-O-(C=O)-CH2-CH3; -CH2-O-(C=O)-(CH2)3-CH3; -CH2-O-(C=O)- (CH2)4-CH3; -CH2-O-(C=O)-(CH2)5-CH3 ; -CH2-O-(C=O)-C(CH3)3; -CH2-O-(C=O)-phe- nyl; -C(=O)-OCH3; C(=O)-O-(CH2)2CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3;-C(=O)-OCH2-CH(CH3)2; -C(=O)-OCH(CH3)2; -C(=O)-O-CH2- CCl3; -C(=O)-OC(CH3)3; -C(=O)-O-(CH2)6-CH3; -C(=O)-O-CH2-CH=CH; -C(=O)-O- CH2-C≡CH; -C(=O)O-phenyl; -C(=O)-O-CH2-phenyl; -CH2-C(=O)-OCH3; -CH2-C(=O)- OCH2-CH3; -CH2-C(=O)-O-(CH2)2-CH3; -CH2-C(=O)-O-(CH2)3-CH3; -CH2-C(=O)-O- (CH2)4-CH3; -CH2-C(=O)-O-(CH2)5-CH3; -CH2-C(=O)-OC(CH3)3; -CH2-C(=O)-O-CH2- CH=CH; -CH2-C(=O)-O-CH=CH-CH3; -C(=O)-NH2; -C(=O)-NH-CH3; -C(=O)-N- (CH3)2; -C(=O)-pyridyl; -C(=O)-pyrimidinyl; -C(=S)-NH2; -C(=S)-NH-CH3; -C(=S)-N- (CH3 ) 2; -C(=S)-pyridyl; -C(=S)-pyrimidinyl; -S(=O)2-CH3; -S(=O)2-CH2-CH3; -S(=O)2- (CH2)2-CH3; -S(=O)2-(CH2)2-CH3; -S(=O)2-tertbutyl; -S(=O)2-phenyl; wherein, cyclo- propyl, phenyl, pyridyl and pyrimidinyl is unsubstituted or substituted with 1, 2 or 3, substituents independently of each other selected from the group consisting of F, Cl, Br, I, methyl, ethyl, propyl, butyl, isopropyl, isobutyl and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -C(=O)-O-CH3; - C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4- CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH-(CH3)2; -C(=O)-O-C(CH3)3; methyl, ethyl, propyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl, tert butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl; wherein alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde pendently of each other selected from the group consisting of Cl, Br, F, I, CN, -OH, - SH, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phe- nyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -CH2-C(=O)-O-C1-C6-alkyl, -C(=O)- NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -NH-C(=O)-C(CH3)3, -S(=O)-C1-C6- alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -NH-SO2- phenyl, -N(CH3)-SO2-phenyl, -CF3, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phe- nyl)3, phenyl and -CH2-phenyl; wherein, the cycloalkyl or cycloalkenyl are unsubsti- tuted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, se- lected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, - O-CH3, -O-C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2- C(=O)-OCH3, -NH-C(=O)-CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R3 is selected from the group consisting of Cl; F; Br; I; CN; -OCH3; -C(=O)-O-CH3; - C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4- CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, oxetanyl, piperidinyl, piper- azinyl, morpholinyl, thiomorpholinyl, 1,2,4-oxadiazolyl, 1,3,4-trimethyl piperazinyl, 2,3-dihydrofuranyl, 2,3-dihydrothienyl, 2,3-dihydropyrrolyl, 2,3-dihydroisoxazolyl, 1,4- dihydropyridin-1-yl, dihydropyranyl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihy- drooxazol-3-yl and 3,4-dihydrooxazol-4-yl; wherein, alkyl, alkenyl and alkynyl are in- dependently of each other unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN; - OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -NO2; -NH2; -NH(CH3)2; wherein, the cyclo- alkyl, cycloalkenyl, heterocycloalkyl and heterocycloalkenyl are unsubstituted or sub- stituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH- C(=O)-CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; methyl, ethyl, pro- pyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, tetrahydro- furanyl, tetrahydrothiophenyl, tetrahydropyranyl, oxetanyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, 1,2,4-oxadiazolyl, 1,3,4-trimethyl piperazinyl, 2,3-dihy- drofuranyl, 2,3-dihydrothienyl, 2,3-dihydropyrrolyl, 2,3-dihydroisoxazolyl, 1,4-dihydro- pyridin-1-yl, dihydropyranyl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihy- drooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl and 3,4-dihydrooxazol-4-yl; wherein, alkyl and alkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN; CF3; CCl3; CHF2; CF2 CF3; C( O) O CH3; C( O) O CH2-CH3; -NO2; -NH2 and -NH(CH3)2; and wherein, the cycloalkyl, cycloalkenyl, het- erocycloalkyl and heterocycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R71, R72, R73 and R74, are independently of each other, selected from the group consisting of H; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; oxo; -C(=O)NH2; - CH(=N-OH); -CH(=N-OCH3); -CH(=N-OCH2CH3); -CH(=N-O(CH2)2CH3); -CH(=N- O(CH2)4CH3); -C(CH3)(=N-OH); -C(CH3)(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -O- CH3; -O-CH2-CH3; -O(CH2)2CH3; -O(CH2)3CH3; -O(CH2)4CH3; -O(CH2)5CH3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1-propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; cyclobutyl; cyclopen- tyl; cyclopropenyl; cyclobutenyl; cyclopentenyl; cyclohexenyl; oxetanyl; piperidinyl; pi- perazinyl; morpholinyl; thiomorpholinyl; 1,2,4-oxadiazolyl; 1,3,4-trimethyl piperazinyl; 2,3-dihydrofuranyl; 2,3-dihydrothienyl; 2,3-dihydropyrrolyl; 2,3-dihydroisoxazolyl and 2,3-dihydrooxazol-2-yl; and wherein, alkyl, alkenyl and alkynyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of F, Cl, -CN, -OH, -NH2, -C(=O)-OH, -C(=O)-OCH3, -Si-(CH3)3, -Si-(C2H5)3, -Si-(CH3)2-phe- nyl, -Si-(phenyl)3, phenyl and -CH2-phenyl; and wherein, the cycloalkyl, cycloalkenyl, heterocycloalkyl and heterocycloalkenyl are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O- C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)- OCH3, -NH-C(=O)-CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl. In another embodiment, the present invention provides a compound of formula (I) is a compound of formula I(A),
formula I(A)
Figure imgf000071_0001
or each compound in the form of a stereoisomer, an agriculturally acceptable salt, a prodrug, a tautomer, an isotopic form, a N-oxide or a S-oxide thereof. In another embodiment, the present invention provides the compound of formula I(A), wherein, R1 is selected from the group consisting of hydrogen, -NH2; -CH2-OH; -CH2-OCH3; -CH2- O-(CH2)2-Si-(CH3)3; -C(=O)-OCH3; -C(=O)-CH=CH-CH3; -C(=O)O-phenyl; -C(=O)-O- CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; - C( O) O (CH2)5 CH3; C( O) O CH2 phenyl; C( O) O CH2 phenyl; C( O) O CH2 CH=CH; -C(=O)-OC(CH3)3; -CH2C(=O)-OCH3; -S(O)2-phenyl; -S(O)2-CF3; -S-phenyl and -C(=O)-NH2; wherein phenyl is substituted with F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen, Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2;
-CF2-CF3; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -C(=O)-O- (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; - C(=O)-O-C(CH3)3; R3 is selected from the group consisting of Cl; F; Br; I; -CN; -O-CH3; -O-CH2-CH3; - C(CH3)2-OH; -CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O- CH(CH3)2; -C(=O)-O-C(CH3)3; -CF2-CF3; methyl, ethyl, propyl, butyl, isopropyl, isobu- tyl, tert butyl, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; and the R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; -CF3; -CHF2; -CH(F)-CF3; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl and tert butyl; or R5 is selected from the group consisting of F; Cl; Br; I; CN; -CF3; -CHF2; -CH(F)- CF3; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl and tert butyl; and the R3 is independently of each other is selected from the group consisting of Cl; F; Br; I; CN; -CF3; -O-CH3; -O-CH2-CH3; -C(CH3)2-OH; -CHF2; -CH(F)- CF3; -CH(CH3)2-OH; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O- (CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CF2- CF3; methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, ethenyl, propenyl, bu- tenyl, isopropenyl, isobutenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cy- clopentyl and cyclohexyl; R71 is selected from the group consisting of -NH2; F ; -NH-CH3; -N(CH3)2 and -NO2; and the remaining of R72, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; - SH; -C(=O)NH2; -CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); -C(CH3)(=N-OCH3); -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; - C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; -CF3; me- thyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1- propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; and 1,2,4- oxadiazolyl; or R72 is selected from the group consisting of F, Cl, Br and I; and the remaining of R71, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; -C(=O)NH2; - CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); -C(CH3)(=N-OCH3); -C(=O)-O-CH3; - C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O- CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; -CF3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1 propenyl; iso propenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R73 is selected from the group consisting of Cl; F; Br; I; -CN; -NO2; -NH2; -NH-CH3; - N(CH3)2; -C(=O)NH2; -CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); -C(CH3)(=N- OCH3); -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O- (CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; -O-CH2- CH3; -CF3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1-propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; and 1,2,4-oxadiazolyl; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; -NH2; -NH-CH3; - N(CH3)2; and -NO2; or R74 is selected from the group consisting of F; -OH; -CN and -OCH3; and the remain- ing of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; -CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; - C(=O)NH2; -CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); -C(CH3)(=N-OCH3); - C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; - C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; -CF3; me- thyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1- propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; and 1,2,4- oxadiazolyl. In another embodiment, the present invention provides the compound of formula (I), wherein, X is N; Y is CR5 or N
A is selected from the group consisting of:
Figure imgf000073_0001
R1 is hydrogen; R2 is hydrogen; R3 is selected from the group consisting of Cl; F; Br; I; -CN;
-O-CH3; -C(CH3)2-OH; -CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; - C(=O)-O-CH3; -CF2-CF3; methyl, ethenyl, isopropenyl, ethynyl and cyclopropyl; and the R5 is hydrogen; or R5 is hydrogen; and the R3 is selected from the group consisting of Cl; F; Br; I; CN; -CF3; -O- CH3; -O-CH2-CH3; -C(CH3)2-OH; -CHF2; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; - C(=O)-O-C(CH3)3; -CF2-CF3; methyl, tert butyl, ethenyl, isopropenyl, ethynyl and cy- clopropyl; R71, R72, R73 and R74 are independently of each other, selected from the group consisting of H; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; oxo; -C(=O)NH2; -CH(=N-OH); - CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -O-CH3; -O(CH2)5CH3; -CF3; methyl; ethynyl; propynyl; butynyl; cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cyclopropenyl; cyclobutenyl; cyclopentenyl; cyclohexenyl; oxetanyl; piperidinyl; piperazinyl; morpholinyl; thiomorpholinyl; 1,2,4-oxadiazolyl. In an embodiment, the present invention provides the compound of formula I(A), wherein the compound is: 3-[5-(trifluoromethyl)isothiazol-4-yl]-1H-indole-5-carbonitrile; 3-[3-(trifluoro- methyl)isothiazol-4-yl]-1H-indole-5-carbonitrile; 3-(3,5-dimethylisothiazol-4-yl)-1H-indole-5-car- bonitrile; and 3-(5-methylthiadiazol-4-yl)-1H-indole-5-carbonitrile. In another embodiment, the present invention provides the compound of formula (I), wherein, X is N; Y is CH or N
A is:
Figure imgf000074_0001
R1 is hydrogen; R2 is hydrogen; R3 is -CF3;
R71, R72, R73 and R74 are independently of each other, selected from the group consisting of hy- drogen; Cl; F; Br; I; CN; methyl, ethynyl, propynyl. In another embodiment, the present invention provides the compound of formula (I), wherein, X is N; Y is CH or N
A is:
Figure imgf000074_0002
R1 is hydrogen; R2 is hydrogen; R3 is -CHF2 or CH2F;
R71, R72, R73 and R74 are independently of each other, selected from the group consisting of hy- drogen; Cl; F; Br; I; CN; methyl, ethynyl, propynyl. In another embodiment, the present invention provides an agrochemical mixture comprising at least one compound of formula (I) or in the form of a stereoisomer or an agriculturally accepta- ble salt or a tautomer or an isotopic form or a N-oxide or a S-oxide or a prodrug thereof, and at least one pesticidally active substance selected from the group consisting of herbicides, safen- ers, fungicides, insecticides and plant growth regulators. In another embodiment, the present invention provides a composition comprising at least one compound of formula (I), or in the form of a stereoisomer or an agriculturally acceptable salt or a tautomer or an isotopic form of a N-oxide or a S-oxide or a prodrug thereof, and an auxiliary. In another embodiment, the present invention provides a method for combating phytopatho genic harmful fungi, which process comprises treating the phytopathogenic fungi, the plant, or the plant propagation material selected from seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants to be protected against fungal attack, the stored materials or harvest, or alternately, the locus or soil or soil sub- stituents or surfaces therefrom, with an effective amount of at least one compound of formula (I), an agriculturally acceptable salt thereof or a tautomer or an isotopic form or a N-oxide or a S-oxide or a prodrug. In a fifth embodiment, the present invention encompasses heteroaryl compounds of
formula (I),
Figure imgf000075_0001
formula (I)
wherein,
X denotes CR4 or N;
Y denotes CR5 or N;
A is selected from the group consisting of:
Figure imgf000075_0002
Figure imgf000076_0001
R1 is selected from the group consisting of hydrogen; -(CH2)aOR6; -(CH2)bC(=O)-R7; - C(=O)-(CH2)c-R8; -C(=O)-(CH2)d-OR9; -C(=O)-CR10(=CR11); -C(=O)-(CH2)e-SR12; - (CH2)f-O-C(=O)-R13; -(CH2)g-C(=O)-OR14; -C(=O)-O-(CH2)h-R15; -O-C(=O)-O-(CH2)i- R16; -C(=O)-NR17R18; -C(=S)-NR19R20; -NR21R22; -S(=O)j-R23 and -(CH2)m-O-(CH2)n-Si- (R25)0;
R2 is selected from the group consisting of hydrogen; halogen; CN; -C(=O)-OR14; unsub- stituted or substituted methyl, ethyl, propyl, pentyl, hexyl, heptyl, isopropyl and iso- pentyl; unsubstituted or substituted cycloalkyl and unsubstituted or substituted cyclo- alkenyl;
R3 is selected from the group consisting of hydrogen, halogen; CN; -OR6, -C(=O)-OR14, unsubstituted or substituted alkyl; unsubstituted or substituted heteroalkyl; unsubsti- tuted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or sub- stituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substi- tuted heterocycloalkyl; and unsubstituted or substituted heterocycloalkenyl;
R4 is selected from the group consisting of hydrogen and halogen;
R5 is selected from the group consisting of hydrogen; halogen; CN; unsubstituted or sub- stituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted al- kynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloal kenyl; unsubstituted or substituted heterocycloalkyl and unsubstituted or substituted heterocycloalkenyl;
R6, R7, R8, R9, R10, R11, R12, R13, R15, R16, R17, R18, R19, R20, R21, R22, R23 and R25 are inde- pendently of each other, selected from the group consisting of hydrogen; halogen; CN; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubsti- tuted or substituted alkynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substituted aryl; unsubstituted or substi- tuted -(alkylene)-aryl; unsubstituted or substituted heterocycloalkyl; unsubstituted or substituted heterocycloalkenyl; unsubstituted or substituted heteroaryl;
R14 is selected from the group consisting of halogen; CN; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; un- substituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsub- stituted or substituted aryl; unsubstituted or substituted -(alkylene)-aryl; unsubstituted or substituted heterocycloalkyl; unsubstituted or substituted heterocycloalkenyl; un- substituted or substituted heteroaryl;
or
R17 together with R18 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
or
R19 together with R20 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
or
R21 together with R22 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37, R39, R40, R41, R42, R44, R46, R47, R48, R50, R52, R53, R55, R56, R58, R59, R60, R61, R62, R63, R65, R66, R67, R71, R72, R73, R74, R75, R76, R77, R78, R79, R80, R81, R82, R83, R84, R85, R86, R87, R88, R89, R90, R91, R93, R95, R96, R97, R98, R99, R100, R101, R102, R103, R104, R105, R106, R107, R108, R109, R110, R111and R113 are independently of each other, selected from the group consisting of H; halogen; CN; -NO2; -NH2; -OH; -SH; oxo; -(CH2)g-C(=O)-OR14; -C(=O)-NR17R18; -C(=S)- NR19R20; -CR115(=N-OR116); unsubstituted or substituted alkyl; unsubstituted or sub- stituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or substituted het- eroalkyl, heteroalkenyl or heteroalkynyl; unsubstituted or substituted cycloalkyl; un- substituted or substituted cycloalkenyl; unsubstituted or substituted heterocycloalkyl and unsubstituted or substituted heterocycloalkenyl;
R38, R43, R49, R51, R54, R57, R64, R68, R69, R70, R112 and R114 are independently of each other selected from the group consisting of -(CH2)aOR6; -(CH2)bC(=O)-R7; -C(=O)-(CH2)c- R8; -C(=O)-(CH2)d-OR9; -C(=O)-CR10(=CR11); -(CH2)f-O-C(=O)-R13; -(CH2)g-C(=O)- OR14; -C(=O)-O-(CH2)h-R15; -S(=O)j-R23; unsubstituted or substituted alkyl, alkenyl or alkynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloal kenyl; unsubstituted or substituted heterocycloalkyl; and unsubstituted or substituted heterocycloalkenyl;
R115 and R116 are independently of each other selected from the group consisting of H; halo- gen; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubsti- tuted or substituted alkynyl; unsubstituted or unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substituted heterocycloal- kyl; and unsubstituted or substituted heterocycloalkenyl;
and whereby,
if not specified otherwise, the alkyl are straight-chain or branched, and comprise 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms as chain links;
the alkenyl are straight-chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
the alkynyl are straight-chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
the heteroalkyl, heteroalkenyl and heteroalkynyl comprise 1, 2, 3, 4, 5 or 6 carbon atoms and 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from O, N(H) or S as chain links;
if not specified otherwise, the alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl and heteroal- kynyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -OH, -SH, -NH2, -NH(C1-C6)alkyl, -NH- CH(CH3)2, -N(C1-C6-alkyl)2, -N(C1-C6-alkyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)- OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, - CH2-C(=O)-O-C1-C6-alkyl, -C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -NH- C(=O)C(CH3)3, -S(=O)-C1-C6-alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, - S(=O)2-NH2, -NH-SO2-phenyl, -N(CH3)-SO2-phenyl, -C1-C6-alkyl, -Si-(CH3)3, -Si(C2H5)3, -Si- (CH3)2-phenyl, -Si-(phenyl)3, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, oxetanyl, pi- peridinyl, piperazinyl, thiomorpholinyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, oxadi- azolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; wherein, the alkyl, heterocycloalkyl, cycloalkyl, aryl or heteroaryl are themselves unsubsti- tuted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O- C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; the cycloalkyl and cycloalkenyl comprises 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms as ring members;
the heterocycloalkyl and heterocycloalkenyl are 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from the group consisting of O, N(H) and S as ring members;
the cycloalkyl, cycloalkenyl, heterocycloalkyl or heterocycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -C(=O)-H, - C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phenyl, -C(=O)-NH2, - C(=O)-NH(C1-C6)alkyl, -NH-C(=O)C(CH3)3, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2- NH2, C1 C6 alkyl, CF3, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, furyl, oxazolyl, thi azolyl, pyrazolyl, thiophenyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, py- razinyl, phenyl and -CH2-phenyl; wherein the alkyl, cycloalkyl, heterocycloalkyl, aryl or het- eroaryl, are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of F, Cl, Br, I, -CN, -NH2, -CF3, -OH, -SH, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, -OCH3, -O-C2H5, phenyl and -CH2-phenyl;
the aryl are mono-, bicyclic or tricyclic and comprise 6, 10 or 14 carbon atoms;
the heteroaryl are mono- or bicyclic and 5- or 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently selected from the group consisting of O, N(H) or S as ring members;
the aryl or heteroaryl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -OH, -SH, -O-CH3, -O-C2H5, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -N(C1-C6-alkyl)2, -N(C1-C6-al- kyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O- phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, - C(=O)-NH-phenyl, -S(=O)-C1-C6-alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -NH-SO2-phenyl, -N(CH3)-SO2-phenyl, -C1-C6-alkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, 1, 2, 4-oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; wherein the alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl.
a is 0, 1, 2 or 3;
b is 0, 1, 2 or 3;
c is 0, 1, 2 or 3;
d is 0, 1, 2 or 3;
e is 0, 1, 2 or 3;
f is 0, 1, 2 or 3;
g is 0, 1, 2 or 3;
h is 1, 2 or 3;
i is 1, 2 or 3;
j is 0, 1, 2 or 3;
k is 0, 1, 2 or 3;
l is 0, 1, 2 or 3;
m is 0, 1, 2 or 3;
n is 0, 1, 2 or 3;
o is 1, 2 or 3;
and
whereby, the following compounds are excluded: [3-(1H-indol-3-yl)-2-thienyl]methanamine; 4- (1-methylindol-3-yl)thiazole-5-carbonitrile; 4-(1H-indol-3-yl)thiazole-5-carbonitrile; ethyl 2- [3-(thiadiazol-4-yl)indol-1-yl]acetate; 1-(benzenesulfonyl)-3-(3-thienyl)indole; 1-(4-nitro- phenyl)sulfonyl-3-(3-thienyl)indole; 1-(p-tolylsulfonyl)3-(3-thienyl)indole; 5-methoxy-3-(3- thienyl) 1H indole; 4 (1H indol 3 yl)isothiazole; ethyl 5,6 dimethoxy 3 (3 thienyl) 1H indole 2-carboxylate; ethyl 5-chloro-3-thiazol-4yl-1H-indole-2-carboxylate; ethyl 5-chloro-3-(3- thienyl)-1H-indole-2-carboxylate; 3-(3-thienyl)-1H-indol-6-amine; 2-methyl-3-(3-thienyl)-1H- indole; 3-(3-thienyl)-1H-indole; 4-(1H-indol-3-yl)thiazole; 4-(1H-indol-3-yl)thiadiazole; 4-(5- cyclohexyl-1H-pyrrolo[2,3-b]pyridine-3yl)thiazole; 4-[1-(benzenesulfonyl)-5-cyclohexyl-pyr- rolo[2,3-b]pyridine-3yl)thiazole and 2-methyl-3-(3-thienyl)-1H-pyrrolo[2,3-b]pyridine or each compound in the form of one or more stereoisomers, agriculturally acceptable salts, prodrugs, tautomers, isotopic forms, N-oxides, S-oxides or a mixture thereof. In an embodiment, the present invention encompasses the compounds of formula (I), wherein, X denotes CR4 and Y denotes CR5; or
X denotes N and Y denotes CR5; or
X denotes CR4 and Y denotes N; or
X denotes N and Y denotes N;
A is as defined in the fifth embodiment;
R1 is selected from the group consisting of hydrogen; -CH2-OH; -CH2-OCH3; -CH2-O- CH(CH3)2; -CH2-O-(CH2)2-Si(CH3)3; -C(=O)-CH3; -C(=O)-CH2-CH3; -(C=O)-(CH2)2- CH3; -(C=O)-(CH2)3-CH3; -(C=O)-(CH2)3-CH3; -(C=O)-(CH2)4-CH3; -(C=O)-(CH2)5- CH3; -C(=O)-C(CH3)3; -C(=O)-CH2-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-cyclopropyl; - C(=O)-phenyl; -C(=O)-CH2-CH3; -C(=O)-(CH2)2-CH3; -C(=O)-(CH2)3-CH3; -C(=O)- (CH2)4-CH3; -C(=O)-(CH2)5-CH3; -C(=O)-CH2-cyclopropyl; -C(=O)-CH2-phenyl; -CH2- O-(C=O)-CH3; -CH2-O-(C=O)-CH2-CH3; -CH2-O-(C=O)-(CH2)3-CH3; -CH2-O-(C=O)- (CH2)4-CH3; -CH2-O-(C=O)-(CH2)5-CH3 ; -CH2-O-(C=O)-C(CH3)3; -CH2-O-(C=O)-phe- nyl; -C(=O)-OCH3; C(=O)-O-(CH2)2CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3;-C(=O)-OCH2-CH(CH3)2; -C(=O)-OCH(CH3)2; -C(=O)-O-CH2- CCl3; -C(=O)-OC(CH3)3; -C(=O)-O-(CH2)6-CH3; -C(=O)-O-CH2-CH=CH; -C(=O)-O- CH2-C≡CH; -C(=O)O-phenyl; -C(=O)-O-CH2-phenyl; -CH2-C(=O)-OCH3; -CH2-C(=O)- OCH2-CH3; -CH2-C(=O)-O-(CH2)2-CH3; -CH2-C(=O)-O-(CH2)3-CH3; -CH2-C(=O)-O- (CH2)4-CH3; -CH2-C(=O)-O-(CH2)5-CH3; -CH2-C(=O)-OC(CH3)3; -CH2-C(=O)-O-CH2- CH=CH; -CH2-C(=O)-O-CH=CH-CH3; -C(=O)-NH2; -C(=O)-NH-CH3; -C(=O)-N- (CH3)2; -C(=O)-pyridyl; -C(=O)-pyrimidinyl; -C(=S)-NH2; -C(=S)-NH-CH3; -C(=S)-N- (CH3)2; -C(=S)-pyridyl; -C(=S)-pyrimidinyl; -S(=O)2-CH3; -S(=O)2-CH2-CH3; -S(=O)2- (CH2)2-CH3; -S(=O)2-(CH2)2-CH3; -S(=O)2-tertbutyl; -S(=O)2-phenyl; wherein, cyclo- propyl, phenyl, pyridyl and pyrimidinyl is unsubstituted or substituted with 1, 2 or 3, substituents independently of each other selected from the group consisting of F, Cl, Br, I, methyl, ethyl, propyl, butyl, isopropyl, isobutyl and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -C(=O)-O-CH3; - C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4- CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH-(CH3)2; -C(=O)-O-C(CH3)3; methyl, ethyl, propyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl, tert butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl; wherein alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde pendently of each other selected from the group consisting of Cl, Br, F, I, CN, -OH, - SH, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phe- nyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -CH2-C(=O)-O-C1-C6-alkyl, -C(=O)- NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -NH-C(=O)-C(CH3)3, -S(=O)-C1-C6- alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -NH-SO2- phenyl, -N(CH3)-SO2-phenyl, -CF3, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phe- nyl)3, phenyl and -CH2-phenyl; wherein, the cycloalkyl or cycloalkenyl are unsubsti- tuted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, se- lected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, - O-CH3, -O-C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2- C(=O)-OCH3, -NH-C(=O)-CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R3 is selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -OCH3; -C(=O)-O- CH3; -C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O- (CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, ethenyl, propenyl, butenyl, isopro- penyl, isobutenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopentyl, cy- clohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, oxetanyl, piperi- dinyl, piperazinyl, morpholinyl, thiomorpholinyl, 1,2,4-oxadiazolyl, 1,3,4-trimethyl pi- perazinyl, 2,3-dihydrofuranyl, 2,3-dihydrothienyl, 2,3-dihydropyrrolyl, 2,3-dihydroisox- azolyl, 1,4-dihydropyridin-1-yl, dihydropyranyl, 2,3-dihydrooxazol-2-yl, 2,3-dihydroox- azol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4- dihydrooxazol-3-yl and 3,4-dihydrooxazol-4-yl; wherein, alkyl, alkenyl and alkynyl are independently of each other unsubstituted or substituted with 1, 2, 3, 4 or 5 substitu- ents independently of each other selected from the group consisting of Cl, Br, F, I, CN; -OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -NO2; -NH2; -NH(CH3)2; wherein, the cycloalkyl, cycloalkenyl, heterocycloalkyl and heterocycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O- C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)- OCH3, -NH-C(=O)-CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R4 is selected from the group consisting of hydrogen; F; Cl; Br and I; R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; methyl, ethyl, pro- pyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, tetrahydro- furanyl, tetrahydrothiophenyl, tetrahydropyranyl, oxetanyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, 1,2,4-oxadiazolyl, 1,3,4-trimethyl piperazinyl, 2,3-dihy- drofuranyl, 2,3-dihydrothienyl, 2,3-dihydropyrrolyl, 2,3-dihydroisoxazolyl, 1,4-dihydro- pyridin-1-yl, dihydropyranyl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihy- drooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl and 3,4 dihydrooxazol 4 yl; wherein, alkyl and alkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2; -CF2-CF3; -C(=O)-O-CH3; -C(=O)-O- CH2-CH3; -NO2; -NH2 and -NH(CH3)2; and wherein, the cycloalkyl, cycloalkenyl, het- erocycloalkyl and heterocycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37, R39, R40, R41, R42, R44, R46, R47, R48, R50, R52, R53, R55, R56, R58, R59, R60, R61, R62, R63, R65, R66, R67, R71, R72, R73, R74, R75, R76, R77, R78, R79, R80, R81, R82, R83, R84, R85, R86, R87, R88, R89, R90, R91, R93, R95, R96, R97, R98, R99, R100, R101, R102, R103, R104, R105, R106, R107, R108, R109, R110, R111 and R113 are independently of each other, selected from the group consisting of H; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; oxo; -C(=O)NH2; -CH(=N-OH); - CH(=N-OCH3); -CH(=N-OCH2CH3); -CH(=N-O(CH2)2CH3); -CH(=N-O(CH2)4CH3); - C(CH3)(=N-OH); -C(CH3)(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -O-CH3; -O-CH2- CH3; -O(CH2)2CH3; -O(CH2)3CH3; -O(CH2)4CH3; -O(CH2)5CH3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1-propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; cyclobutyl; cyclopentyl; cyclopro- penyl; cyclobutenyl; cyclopentenyl; cyclohexenyl; oxetanyl; piperidinyl; piperazinyl; morpholinyl; thiomorpholinyl; 1,2,4-oxadiazolyl; 1,3,4-trimethyl piperazinyl; 2,3-dihy- drofuranyl; 2,3-dihydrothienyl; 2,3-dihydropyrrolyl; 2,3-dihydroisoxazolyl and 2,3-dihy- drooxazol-2-yl; and wherein, alkyl, alkenyl and alkynyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of F, Cl, -CN, -OH, -NH2, -C(=O)-OH, -C(=O)-OCH3, -Si-(CH3)3, -Si-(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phe- nyl)3, phenyl and -CH2-phenyl; and wherein, the cycloalkyl, cycloalkenyl, heterocyclo- alkyl and heterocycloalkenyl are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group con- sisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)- CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH-C(=O)- CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R38, R43, R49, R51, R54, R57, R64, R68, R69, R70, R112 and R114 are independently of each other selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert butyl; wherein, the alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of F, Cl, , Br, I, -CN, -CF3, -CN, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-OH, -C(=O)-OCH3, -Si-(CH3)3, -Si- (C2H5)3, -Si-(CH3)2-phenyl, -Si-(phenyl)3, phenyl and -CH2-phenyl.
In an embodiment, the present invention encompasses compounds, wherein the
compound of formula (I) is a compound of formula I(A),
Figure imgf000083_0001
wherein,
X and Y are as defined in the fifth embodiment;
R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R25, R71, R72, R73 and R74, a, b, c, d, e, f, g, h, I, j, k, l, m, n and o are as defined in the fifth embodiment;
or each of the compounds in the form of one or more stereoisomers, agriculturally accepta- ble salts, prodrugs, tautomers, isotopic forms, N-oxides or S-oxides thereof. In another embodiment, the present invention encompasses the compounds of formula I(A), wherein, R1 is selected from the group consisting of hydrogen; -CH2-OH; -CH2-OCH3; -CH2-O- CH(CH3)2; -CH2-O-(CH2)2-Si(CH3)3; -C(=O)-CH3; -C(=O)-CH2-CH3; -C(=O)-C(CH3)3; - C(=O)-CH2-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-phenyl; -C(=O)-cyclopropyl; -C(=O)- CH2-CH3; -C(=O)-(CH2)2-CH3; -C(=O)-(CH2)3-CH3; -C(=O)-(CH2)4-CH3; -C(=O)- (CH2)5-CH3; -C(=O)-CH2-cyclopropyl; -C(=O)-CH2-phenyl; -CH2-O-(C=O)-CH3; -CH2- O-(C=O)-CH2-CH3; -CH2-O-(C=O)-(CH2)3-CH3; -CH2-O-(C=O)-(CH2)4-CH3; -CH2-O- (C=O)-(CH2)5-CH3; -CH2-O-(C=O)-C(CH3)3; -CH2-O-(C=O)-phenyl; -C(=O)-OCH3; - C(=O)-OCH2CH3; C(=O)-O-(CH2)2CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3;-C(=O)-O-CH2-CH(CH3)2; -C(=O)-O-CH(CH3)2; -C(=O)-O-CH2- CCl3; -C(=O)-OC(CH3)3; -C(=O)-O-(CH2)6-CH3; -C(=O)-O-CH2-CH=CH; -C(=O)-O- CH2-C≡CH; -C(=O)O-phenyl; -C(=O)-O-CH2-phenyl; -CH2-C(=O)-OCH3; -CH2-C(=O)- OCH2-CH3; -CH2-C(=O)-O-(CH2)2-CH3; -CH2-C(=O)-O-(CH2)3-CH3; -CH2-C(=O)- O(CH2)4-CH3; -CH2-C(=O)-O-(CH2)5-CH3; -CH2-C(=O)-O-C(CH3)3; -CH2-C(=O)-O- CH2-CH=CH; -CH2-C(=O)-O-CH=CH-CH3; -C(=O)-NH2; -C(=O)-NH-CH3; -C(=O)-N- (CH3 ) 2; -C(=O)-pyridyl; -C(=O)-pyrimidinyl; -C(=S)-NH2; -C(=S)-NH-CH3; -C(=S)-N- (CH3 ) 2; -C(=S)-pyridyl; -C(=S)-pyrimidinyl; -S(=O)2-CH3; -S(=O)2-CH2-CH3; -S(=O)2- (CH2)2-CH3; -S(=O)2-(CH2)2-CH3; -S(=O)2-tertbutyl; -S(=O)2-phenyl; wherein, cyclo- propyl, phenyl, pyridyl and pyrimidinyl is unsubstituted or substituted with 1, 2 or 3, substituents independently of each other selected from the group consisting of F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -C(=O)-O-CH3; - C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5- CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; methyl, ethyl, propyl, hexyl, heptyl, iso- propyl, isobutyl, isopentyl, tert butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl; wherein alkyl is unsub- stituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, F, Br, I, CN, OH, SH, C( O) H, C( O) C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phenyl, -CH2-C(=O)-OH, - CH2-C(=O)-O-C1-C6-alkyl, -C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, - S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2- phenyl, -Si-(phenyl)3, phenyl and -CH2-phenyl; wherein, the cycloalkyl or cycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, - CH2-C(=O)-OCH3, -NH-C(=O)-CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopro- pyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R3 is selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -O-CH3; -O-CH2- CH3; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3- CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O- C(CH3)3; methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl; wherein, alkyl, alkenyl or alkynyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -NO2; -NH2; -NH(CH3)2; wherein, the cy- cloalkyl, and cycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substit- uents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH-C(=O)-CH3, -NH-C(=O)- C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2- phenyl; R4 is selected from the group consisting of hydrogen; F; Cl; Br and I; R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; methyl, ethyl, pro- pyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl; wherein, alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of Cl, Br, F, I, CN; -C(=O)- O-CH3; -C(=O)-O-CH2-CH3; -NO2; -NH2; -NH(CH3)2; and wherein, the cycloalkyl and cycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, propyl, isopropyl, butyl, iso- butyl, tert butyl, phenyl and -CH2-phenyl; R71, R72, R73 and R74 are independently of each other, selected from the group consisting of H; Cl; F; Br; I; -CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; -C(=O)NH2; -CH(=N- OH); -CH(=N-OCH3); -CH(=N-OCH2CH3); -CH(=N-O(CH2)2CH3); -CH(=N- O(CH2)4CH3); -C(CH3)(=N-OH); -C(CH3)(=N-OCH3); -C(=O)-O-CH3; -C(=O)-O- (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; - C( O) O C(CH3)3; CH C(CN)2; OCH3; O CH2 CH3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1-propenyl; isopropenyl; isobu- tenyl; ethynyl; propynyl; butynyl; cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cy- clopropenyl; cyclobutenyl; cyclopentenyl; cyclohexenyl; oxetanyl; piperidinyl; piper- azinyl; morpholinyl; thiomorpholinyl; 1,2,4-oxadiazolyl; 1,3,4-trimethyl piperazinyl; 2,3-dihydrofuranyl; 2,3-dihydrothienyl; 2,3-dihydropyrrolyl; 2,3-dihydroisoxazolyl and 2,3-dihydrooxazol-2-yl; and wherein, alkyl, alkenyl and alkynyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of F, Cl, -CN, -OH, -NH2, -C(=O)-OH, -C(=O)-OCH3, -Si-(CH3)3, -Si-(C2H5)3, -Si-(CH3)2-phe- nyl, -Si-(phenyl)3, phenyl and -CH2-phenyl; and wherein, the cycloalkyl, cycloalkenyl, heterocycloalkyl and heterocycloalkenyl are independently of each other unsubsti- tuted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, - CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH-C(=O)-CH3, - NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl.
In a preferred embodiment, the present invention encompasses the compounds of formula I(A), wherein, R1 is selected from the group consisting of hydrogen; -NH2; -CH2-OH; -CH2-OCH3; -CH2- O-(CH2)2-Si-(CH3)3; -C(=O)-OCH3; -C(=O)-CH=CH-CH3; -C(=O)O-phenyl; -C(=O)-O- CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; - C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH2-phenyl; -C(=O)-O-CH2-phenyl; -C(=O)-O-CH2- CH=CH; -C(=O)-OC(CH3)3; -CH2C(=O)-OCH3; -S(O)2-phenyl; -S(O)2-CF3; -S-phenyl and -C(=O)-NH2; wherein phenyl is substituted with F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2;
-CF2-CF3; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -C(=O)-O- (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; - C(=O)-O-C(CH3)3; R3 is selected from the group consisting of Cl; F; Br; I; -CN; -O-CH3; -O-CH2-CH3; - C(CH3)2-OH; -CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O- CH(CH3)2; -C(=O)-O-C(CH3)3; -CF2-CF3; methyl, ethyl, propyl, butyl, isopropyl, isobu- tyl, tert butyl, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; and the remaining of R4 and R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; -CF3; - CHF2; -CH(F)-CF3; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobu- tyl, isopentyl and tert butyl; or R4 is selected from the group consisting of F; Cl; Br and I; and the remaining of R3 and R5 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; -O-CH2-CH3; -C(CH3)2-OH; -CHF2; -CH(F)-CF3; - CH(CF3) OH; C( O) O CH3; C( O) O (CH2)3 CH3; C( O) O (CH2)4 CH3; C( O) O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CF2-CF3; methyl, ethyl, pro- pyl, butyl, isopropyl, isobutyl, tert butyl, ethenyl, propenyl, butenyl, isopropenyl, iso- butenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclo- hexyl; R71 is selected from the group consisting of -NH2; F ; -NH-CH3; -N(CH3)2 and -NO2; and the remaining of R72, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; - SH; -C(=O)NH2; -CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); -C(CH3)(=N-OCH3); -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; - C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; -CF3; me- thyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1- propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; and 1,2,4- oxadiazolyl; or R72 is selected from the group consisting of F, Cl, Br and I; and the remaining of R71, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; -C(=O)NH2; - CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); -C(CH3)(=N-OCH3); -C(=O)-O-CH3; - C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O- CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; -CF3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1-propenyl; iso- propenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R73 is selected from the group consisting of Cl; F; Br; I; -CN; -NO2; -NH2; -NH-CH3;
-N(CH3)2; -C(=O)NH2; -CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); -C(CH3)(=N- OCH3); -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O- (CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; -O-CH2- CH3; -CF3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1-propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; and 1,2,4-oxadiazolyl; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; -NH2; -NH-CH3; - N(CH3)2; and -NO2; or R74 is selected from the group consisting of F; -OH; -CN and -OCH3; and the re- maining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; -CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; - C(=O)NH2; -CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); -C(CH3)(=N-OCH3); - C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; - C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; -CF3; me- thyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1- propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; and 1,2,4- oxadiazolyl. In a further preferred embodiment, the present invention encompasses the compounds of formula I(A), wherein, R1 is selected from the group consisting of hydrogen; -NH2; -CH2-OH; -CH2-OCH3; -CH2- O-(CH2)2-Si-(CH3)3; -C(=O)-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-O-phenyl; -C(=O)-O- CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; - C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH2-phenyl; -C(=O)-O-CH2-phenyl; -C(=O)-O-CH2- CH=CH; -C(=O)-OC(CH3)3; -CH2C(=O)-OCH3; -S(O)2-phenyl; -S(O)2-CF3; -S-phenyl and -C(=O)-NH2; wherein phenyl is substituted with F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2;
-CF2-CF3; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -C(=O)-O- (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; - C(=O)-O-C(CH3)3; R3 is selected from the group consisting of Cl; F; Br; I; -CN; -O-CH3; -C(CH3)2-OH; - CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)-O-CH3; -CF2-CF3; me- thyl, ethenyl, isopropenyl, ethynyl and cyclopropyl; and the remaining of R4 and R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; -CF3; -CHF2; -CH(F)- CF3; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl and tert butyl; or R4 is selected from the group consisting of F; Cl; Br and I; and the remaining of R3 and R5 are independently of each other selected from the group consisting of hydro- gen; Cl; F; Br; I; CN; -CF3; -O-CH3; -C(CH3)2-OH; -CHF2; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -CF2-CF3; methyl, ethenyl, isopropenyl, ethynyl, and cyclopropyl; or R5 is selected from the group consisting of F; Cl; Br; I; CN; -CF3; -CHF2; -CH(F)- CF3; methyl; and the remaining of R3 and R4 are independently of each other is se- lected from the group consisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; -O-CH2- CH3; -C(CH3)2-OH; -CHF2; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O- C(CH3)3; -CF2-CF3; methyl, tert butyl, ethenyl, isopropenyl, ethynyl and cyclopropyl; R71 is selected from the group consisting of -NH2; F and -NO2; and the remaining of R72, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; -C(=O)NH2; - CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; - CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R72 is selected from the group consisting of F, Cl, Br and I; and the remaining of R71, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; -C(=O)NH2; - CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R is selected from the group consisting of Cl; F; Br; I; CN; NO2; C( O)NH2; CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; -NH2; and -NO2; or R74 is selected from the group consisting of F; -OH; -CN and -OCH3; and the re- maining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; -CN; -NO2; -OH; -SH; -C(=O)NH2; -CH(=N-OH); - CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl.
In a further specific embodiment, the present invention encompasses the compounds of formula I (A), wherein, R1 is selected from the group consisting of hydrogen; -NH2; -CH2-OH; -CH2-OCH3; -CH2- O-(CH2)2-Si-(CH3)3; -C(=O)-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-O-phenyl; -C(=O)-O- CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; - C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH2-phenyl; -C(=O)-O-CH2-phenyl; -C(=O)-O-CH2- CH=CH; -C(=O)-OC(CH3)3; -CH2C(=O)-OCH3; -S(O)2-phenyl; -S(O)2-CF3; -S-phenyl and -C(=O)-NH2; wherein phenyl is substituted with F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2;
-CF2-CF3; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -C(=O)-O- (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; - C(=O)-O-C(CH3)3; R3 is selected from the group consisting of Cl; F; Br; I; -CN; -O-CH3; -C(CH3)2-OH; - CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)-O-CH3; -CF2-CF3; and the remaining of R4 and R5 is selected from the group consisting of hydrogen; -Cl; F; Br; I; CHF2; -CH(F)-CF3 and methyl; or R4 is Cl, F, Br, I; and the remaining of R3 and R5 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -CF3; -O-CH3; -C(CH3)2-OH; - CHF2; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3 and -CF2-CF3; R71 is selected from the group consisting of hydrogen, -NH2; F and -NO2; and the remain- ing of R72, R73 and R74 are independently of each other selected from the group con- sisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; - C(=O)NH2; -CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -O- CH2-CH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R72 is selected from the group consisting of F, Cl, Br and I; and the remaining of R71, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; NO2; NH2; NH CH3; N(CH3)2; OH; SH; C( O)NH2; CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R73 is selected from the group consisting of Cl; F; Br; I; -CN; -NO2; -C(=O)NH2; - CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; -NH2; and -NO2; or R74 is selected from the group consisting of F; -OH; -CN and -OCH3; and the re- maining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; -CN; -NO2; -OH; -SH; -C(=O)NH2; -CH(=N-OH); - CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl.
In a yet further specific embodiment, the present invention encompasses the compounds of formula I(A), wherein, R1 is selected from the group consisting of hydrogen; -NH2; -CH2-OH; -CH2-OCH3; -CH2- O-(CH2)2-Si-(CH3)3; -C(=O)-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-O-phenyl; -C(=O)-O- CH2-phenyl; -C(=O)-O-CH2-phenyl; -C(=O)-O-CH2-CH=CH; -C(=O)-OC(CH3)3; - CH2C(=O)-OCH3; -S(O)2-phenyl; -S(O)2-CF3; -S-phenyl and -C(=O)-NH2; wherein phenyl is substituted with F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2;
-CF2-CF3; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; R3 is selected from the group consisting of Cl; F; Br; I; -CN; -O-CH3; -C(CH3)2-OH; - CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)-O-CH3; -CF2-CF3; and the remaining of R4 and R5 independently of each other is selected from hydrogen; or R4 is hydrogen; and the remaining of R3 and R5 are independently of each other selected from the group consisting of Cl; F; Br; I; CN; -CF3; -O-CH3; -C(CH3)2-OH; -CHF2; - CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3 and -CF2-CF3; R71 is selected from the group consisting of -NH2; F and -NO2; and the remaining of R72, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; -C(=O)NH2; - CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; - CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R72 is selected from the group consisting of F, Cl, Br and I; and the remaining of R71, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; -C(=O)NH2; - CH( N OH); CH( N OCH3); C( O) O CH3; CH C(CN)2; OCH3; CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R73 is selected from the group consisting of Cl; F; Br; I; -CN; -NO2; -C(=O)NH2; - CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; -NH2; and -NO2; or R74 is selected from the group consisting of F; -OH; -CN and -OCH3; and the re- maining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; -CN; -NO2; -OH; -SH; -C(=O)NH2; -CH(=N-OH); - CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl.
In a yet further specific embodiment, the present invention encompasses the compounds of formula I(A), wherein, X is CR4; Y is CR5; R1 is hydrogen; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2;
-CF2-CF3; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; R3 is selected from the group consisting of Cl; F; Br; I; -CN; -O-CH3; -C(CH3)2-OH; - CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)-O-CH3; -CF2-CF3; and the remaining of R4 and R5 independently of each other is selected from hydrogen; or R4 is hydrogen; and the remaining of R3 and R5 are independently of each other selected from the group consisting of Cl; F; Br; I; CN; -CF3; -O-CH3; -C(CH3)2-OH; - CHF2; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3 and -CF2-CF3; or R5 is hydrogen; and the remaining of R3 and R4 are independently of each other is selected from the group consisting of Cl; F; Br; I; CN; -CF3; -O-CH3; -C(CH3)2-OH; - CHF2; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3 and -CF2-CF3. R71 is selected from the group consisting of -NH2; F and -NO2; and the remaining of R72, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; -C(=O)NH2; - CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; - CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R72 is selected from the group consisting of F, Cl, Br and I; and the remaining of R71, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; -C(=O)NH2; - CH( N OH); CH( N OCH3); C( O) O CH3; CH C(CN)2; OCH3; CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R73 is selected from the group consisting of Cl; F; Br; I; -CN; -NO2; -C(=O)NH2; - CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; -NH2; and -NO2; or R74 is selected from the group consisting of F; -OH; -CN and -OCH3; and the re- maining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; -CN; -NO2; -OH; -SH; -C(=O)NH2; -CH(=N-OH); - CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl.
In a further embodiment, the present invention encompasses the compounds of formula I(A), wherein, R1 is selected from the group consisting of hydrogen; -NH2; -CH2-OH; -CH2-OCH3; -CH2- O-(CH2)2-Si-(CH3)3; -C(=O)-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-O-phenyl; -C(=O)-O- CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; - C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH2-phenyl; -C(=O)-O-CH2-phenyl; -C(=O)-O-CH2- CH=CH; -C(=O)-OC(CH3)3; -CH2C(=O)-OCH3; -S(O)2-phenyl; -S(O)2-CF3; -S-phenyl and -C(=O)-NH2; wherein phenyl is substituted with F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2;
-CF2-CF3; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -C(=O)-O- (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; - C(=O)-O-C(CH3)3; R3 is selected from the group consisting of methyl, ethenyl, isopropenyl, ethynyl and cy- clopropyl; and the remaining of R4 and R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; -CF3; -CHF2; -CH(F)-CF3; methyl, ethyl, propyl, butyl, pen- tyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl and tert butyl; or R4 is selected from the group consisting of F; Cl; Br and I; and the remaining of R3 and R5 are independently of each other selected from the group consisting of hydro- gen, methyl, ethenyl, isopropenyl, ethynyl, and cyclopropyl; or R5 is selected from the group consisting of F; Cl; Br; I; F; Cl; Br; I; CN; -CF3; -CHF2;
-CH(F)-CF3; methyl and the remaining of R3 and R4 are independently of each other is selected from the group consisting of hydrogen; methyl, ethenyl, isopropenyl, ethynyl and cyclopropyl. R71 is selected from the group consisting of -NH2; F and -NO2; and the remaining of R72, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; NO2; NH2; NH CH3; N(CH3)2; OH; SH; C( O)NH2; CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; - CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R72 is selected from the group consisting of F, Cl, Br and I; and the remaining of R71, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; -C(=O)NH2; -CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R73 is selected from the group consisting of Cl; F; Br; I; -CN; -NO2; -C(=O)NH2; - CH(=N-OH); -CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; -NH2; and -NO2; or R74 is selected from the group consisting of F; -OH; -CN and -OCH3; and the re- maining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; -CN; -NO2; -OH; -SH; -C(=O)NH2; -CH(=N-OH); - CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; -CF3; methyl; ethynyl; cyclopropyl; and 1,2,4-oxadiazolyl. The compounds of formula (I) can be prepared by standard processes of organic chemistry. The compounds of formula (I) can be prepared according to methods or in analogy to standard tech- niques that are described in the state of art. The synthetic procedure utilises the starting materials that are either commercially available or that may be prepared according to conventional proce- dures starting from readily available compounds. General Procedure:
With due modification of the starting compounds, the compounds of formula I can be prepared by procedures as given in below schemes. Route 1:
Step 1: Halogenation
To a stirred solution of p
Figure imgf000092_0001
rotected amino compound in a polar aprotic solvent such as DCE was added a halogenating agent portion wise at 0oC– rt and stirred for 2-14 hrs at rt. After the com- pletion of the reaction, the mixture was washed with brine, aq. Na2SO3, dried over Na2SO4, fil- tered, concentrated and purified by column to obtain the desired halogenated product. Step 2: Coupling
Figure imgf000093_0001
To a mixture of the N-protected halogenated compound in a non-polar aprotic solvent such as dioxane or a polar aprotic solvent like Acetonitrile, DMF or THF or a solvent mixture such as Dioxane-water or CHsCN-water was added the boronate ester/boronic acid and a base such as K2CO3 in the same solvent.Then the Pd-catalyst such as Pd(dppf)C or similar was added to the reaction mixture and heated to higher temperatures for 4-16 hrs. Additional Pd-catalyst was added in case of incompletion of the reaction and the mixture was stirred for another 6-10 hrs. The reaction was monitored by TLC and LCMS. After the completion of the reaction, the mixture was concentrated and purified by column to obtain a cis and trans isomeric mixture of the coupled product.
Step 3: Cyclization
Figure imgf000093_0002
The coupled product from the previous step in aq. inorganic acid such as 2N HCI was refluxed for 2-10 hrs. Completion of the reaction was monitored by using TLC and LCMS. The mixture was then extracted with ethyl acetate, dried over Na2S04, filtered, concentrated and purified by column chromatography to obtain the desired cyclized product. Route 2:
Step 1 : Aldol condensation
Figure imgf000093_0003
To a polar protic solvent containing a base was added the aldehyde and the azide at at 0 °C and then stirred for 4 -16 hrs. After this time the reaction mixture was concentrated to a slurry and dissolved in a polar aprotic solvent and NH4CI(aq). The aqueous layer was extracted with EtOAc and the combined organic washings were dried (Na2S04) and concentrated in vacuo. The crude product was purified by flash chromatography. Step 2: cyclization
Figure imgf000094_0001
A solution of above azide product in a high-boiling solvent was heated to higher tempetatures for 1 -16 hrs, then cooled to room temperature and concentrated in vacuo to afford the crude product which was purified by column chromatography.
Subsequent functionalization of the ring:
lodination
Figure imgf000094_0002
To a solution of protected or unprotected (aza)indoles or the 5,5-ring system in a polar aprotic solvent such as DMF or a protic solvent like methanol or a polar solvent mixture such as methanol-water system at rt was added the halogenating agent portion wise over a period of 15- 30 min. Reaction mixture was stirred for 2 - 16 hrs at rt. The reaction progress was monitored by TLC and LCMS. After completion of the reaction, the solvent was evaporated and the residue was diluted in ethyl acetate and washed with H2O followed by brine wash. Organic layer was separated and dried over Na2S04 and concentrated to afford the crude compound which was used for the next step without further purification.
Protection of the (aza)indole or 5,5-ring NH group
Figure imgf000094_0003
To a solution of substituted (aza)indole in a polar aprotic solvent such as THF was added the base over period of 10 - 20 minutes at 0°C under an inert gas. Reaction mixture was stirred at the same temperature for 30 minutes and to this reaction mixture was added the halide of the protecting group (for example tosyl chloride) over a period of 15 minutes. Reaction was continued for 2 - 16 hrs at rt and the completion was monitored by TLC and LCMS. Reaction mixture was cooled to 0°C and quenched with sat. NH4CI solution and diluted with ethyl acetate. Organic layer was separated and washed first with water followed by a brine wash. Organic layer was dried over Na2S04 and concentrated under vacuum. The crude compound was further purified by chromatography or by trituration with ethyl acetate/heptane mixture.
Coupling of halo(aza)indole/5,5-ring system with boronic acid/boronate ester: To a
Figure imgf000095_0001
solution of halo(aza)indole or similar 5,5-ring system in a commonly used polar sol- vent such as THF or DMF or solvent mixture (eg: Dioxane: H2O, 4:1) was added the boronic acid/boronate ester followed by the addition of a base at rt. The reaction mixture was degassed followed by addition of the palladium catalyst such as Pd(dppf)2Cl2 or similar other catalysts. Re- action mixture was heated at 110oC for 2 - 14 hrs. The reaction completion was monitored by TLC and LCMS. Reaction mixture was cooled to rt, diluted with ethyl acetate and filtered through celite. Organic layer was separated and washed with water, followed by washing with brine. Organic layer was separated, dried over Na2SO4 and concentrated to afford crude product which was further purified by chromatography to afford the pure compound.
N-deprotection:
The N-deprotectio
Figure imgf000095_0002
d on the protecting group. Protecting group-free coupling:
Figure imgf000095_0003
To a solution of halo(aza)indole in a polar solvent such as DMF or THF /solvent mixture such as dioxane:water, was added boronic acid/boronate ester followed by the addition of a base at rt. The solution was degassed followed by the addition of Xphos-Pd-G2 or similar type of Pd- catalyst. Reaction mixture was heated at 110oC for 2– 14 hrs. The reaction was monitored by TLC and LCMS. Reaction mixture was cooled to rt, diluted with ethyl acetate and filtered through celite. Organic layer was separated and washed with water, followed by washing with brine solu- tion. Organic layer was then dried over Na2SO4 and concentrated to afford crude product which was further purified by chromatography to afford pure compound.
Fischer Indole synthesis route for the synthesis of Indole, azaindole or 5,5-ring products:
Figure imgf000096_0001
To a solution of (hetero)arylhydrazine in a polar protic solvent such as ethanol or a aprotic solvent such as THF or an acid such as acetic acid was added the aldehyde or an acetal protected aldehyde (with any ring sized acetal) in the same solvent dropwise. Inorganic acids such as HCl or H2SO4 or organic acids such as acetic acid in stoichiometric or catalytic amounts or even a mixture of of organic and inorganic acids was added to the reaction mixture and heated to reflux for 6-16 hrs. Reaction progress was monitored by TLC and LCMS. After completion of the reac- tion, solvent was evaporated and the residue was diluted in ethyl acetate and washed with H2O followed by brine wash. Organic layer was separated and dried over Na2SO4 and concentrated to afford the crude compound which was further purified by column chromatography.
Note: In some cases, the reaction of (hetero)arylhydrazine and (protected) aldehyde leads to the (hetero)arylhydrazone formation which does not react further. In such cases, the hydrazone was isolated and further taken in a polar protic solvent was added inorganic acids or organic acids or a mixture of acids in stoichiometric or catalytic amounts and heated to reflux for a further 6-16 hrs to obtain the expected cyclized product. Work-up and purification of the final product is the same as mentioned before.
Individual compounds of formula I can also be prepared by derivatisation of other compounds of formula I or the intermediates thereof.
If the synthesis yields mixtures of isomers, a separation is generally not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or dur- ing application (for example under the action of light, acids or bases). Such conversions may also take place after use, for example in the treatment of plants in the treated plant, or in the harmful fungus to be controlled. With respect to their use, particular preference is given to compounds of formula (I) compiled in the tables below. Moreover, the groups mentioned for a substituent in the tables are, by them- seleves and independently of the combination in which they are mentioned, a particularly pre- ferred embodiment of the substituent in question. Compounds of formula (I) in which the combination of R1; R2; R3; R71 and R72 are defined in Table A and the combination of R5; R73 and R74 are defined in Table B as follows:
Figure imgf000097_0001
formula (I) T l A
Figure imgf000097_0002
Figure imgf000098_0001
Figure imgf000099_0001
Figure imgf000100_0001
Figure imgf000101_0001
Figure imgf000102_0001
Figure imgf000103_0001
Figure imgf000104_0001
Figure imgf000105_0001
Figure imgf000106_0001
Figure imgf000107_0001
Figure imgf000108_0001
Figure imgf000109_0001
Figure imgf000110_0001
Figure imgf000111_0005
, ,
Figure imgf000111_0001
formula (I)
wherein the R1; R2; R3; R71 and R72 are as in A.1. and R5; R73 and R74 are as in B.3.
In one embodiment, the compound of formula (I) is
Figure imgf000111_0002
formula (I)
wherein the R1; R2; R3; R71 and R72 are as in A.4. and R5; R73 and R74 are as in B.59.
In one embodiment, the compound of formula (I) is
Figure imgf000111_0003
formula (I)
wherein the R1; R2; R3; R71 and R72 are as in A.380. and R5; R73 and R74 are as in B.19.
Compounds of formula (I) in which the combination of R1; R2; R3; R71 and R72 are defined in Table A and the combination of R73 and R74 are defined in Table C as follows:
Figure imgf000111_0004
formula (I) Table C
1: R74 is H and R73 is -CN.
Figure imgf000112_0001
Figure imgf000113_0001
Figure imgf000114_0004
For example, in one embodiment, the compound of formula (I) is
Figure imgf000114_0001
formula (I)
wherein the R1; R2; R3; R71 and R72 are as in A.1. and R73 and R74 are as in C.3.
In one embodiment, the compound of formula (I) is
Figure imgf000114_0002
formula (I)
wherein the R1; R2; R3; R71 and R72 are as in A.4. and R73 and R74 are as in C.59.
In one embodiment, the compound of formula (I) is
Figure imgf000114_0003
formula (I)
wherein the R1; R2; R3; R71 and R72 are as in A.380. and R73 and R74 are as in C.19.
A skilled person will readily understand that the preferences for the substituents, also in particu- lar the ones given in the tables below for the respective substituents, given herein in connection with compounds I apply for the intermediates accordingly. Thereby, the substituents in each case have independently of each other or more preferably in combination the meanings as de fined herein. In one embodiment, the processes for the preparation of the compounds of formula (I) or the agriculturally acceptable salts, wherein,
A, X, Y, R1, R2 and R3 are as defined in the first to forty nine embodiments hereinabove; comprises the reaction steps as outlined in Process scheme 1 and Process scheme 2 described below, wherein,
Process scheme 1
Figure imgf000115_0001
Reaction conditions:
Step 1a: Potassium iodide (KI), iodine (I) and N-iodosuccinimide; dimethyl formamide (DMF), methanol, ethanol and water; 2- 16 h; RT (room temperature);
Step 1b: Tosyl chloride and tert-butoxycarbonyl anhydride; 2-16 h; 0℃;
Step 1c: Tetrahydrofuran (THF) or DMF; Potassium carbonate (K2CO3) or Na2CO3) or their mix- ture; 2-14 h; 110℃
Step 1d: Sodium hydride (NaH), Sodium methoxide (MeONa) and Sodium ethoxide (EtONa); 1 to 24 h; RT or 0℃ to 90℃; comprises the reaction steps of:
Step 1a:
This process step comprises reacting compound of formula 1-a (wherein A is defined as in twenty seventh to forty nineth embodiments) and R1 is hydrogen; with a halogenating agent se- lected from the group consisting of KI, I and N-iodosuccinimide, in the presence of solvent se- lected from the group consisting of DMF, methanol, ethanol and water to obtain a compound of formula 1-a′. Step 1b:
This process step comprises reacting the compound of formula 1-a′ with a reagent selected from the group consisting of tosyl chloride and tert-butoxycarbonyl anhydride to obtain a com- pound of formula 1-b. Step 1c:
This process step comprises reacting the compound of formula 1-a with compound of for- mula 1-b in the presence of a polar solvent selected from the group consisting of THF and DMF and a base selected from the group consisting of K2CO3 and Na2CO3 to form a compound of formula (1-c′). Step 1d:
This process step comprises reacting the compound of formula 1-c′ in the presence of a base selected from the group consisting of NaH, MeONa and EtONa to obtain a compound of formula (I); wherein R1 is H; Step 1e:
This process step comprises reacting the compound of formula (I) obtained in step (1d) with an appropriate R1 in the presence of a suitable base; to obtain a compound of formula (I), wherein R1 is as defined in the twenty seventh to forty nineth embodiment;
or
if desired, the compound of formula (I) obtained in step (1d) or step (1e) is converted to its agri- culturally acceptable salts;
or alternately,
Process scheme 2:
Figure imgf000116_0001
Reaction conditions:
Step 2a
Methanol (MeOH); ethanol (EtOH); and THF; 6-16h; heated to reflux; comprises the reaction steps of:
Step 2a This process step involves reacting compounds of formula 2 a with a compound of formula 2-b or compound of formula 2-c in the presence of a solvent selected from the group consisting of MeOH, EtOH, and THF and an acid selected from acetic acid, HCl, H2SO4, and trifluoroacetic acid to obtain a compound of formula (I) or to obtain an intermediate of formula I-a. The intermediate is further treated with an acid selected from the group con- sisting of HCl, H2SO4, AcOH and THFto obtain a compound of formula (I). Depending on the substitution pattern, the compounds according to the invention may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers. The invention provides both the single pure enantiomers or pure diastereomers of the compounds according to the invention, and their mixtures and the use according to the invention of the pure enantiomers or pure diastereomers of the compounds according to the in- vention or their mixtures. Suitable compounds according to the invention also include all possible geometrical stereoisomers (cis/trans isomers) and mixtures thereof. Cis/trans isomers may be present with respect to an alkene, carbon-nitrogen double-bond or amide group. The term "ste- reoisomer(s)" encompasses both optical isomers, such as enantiomers or diastereomers, the lat- ter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis/trans isomers). The present invention relates to every possible stereoisomer of the com- pounds of formula I, i.e. to single enantiomers or diastereomers, as well as to mixtures thereof.
The compounds of formula (I) may be amorphous or may exist in one or more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities. The present invention relates to amor- phous and crystalline compounds of formula I, mixtures of different crystalline states of the re- spective compound I, as well as amorphous or crystalline salts thereof.
Salts of the compounds of the formula (I) are preferably agriculturally acceptable salts. They can be formed in a customary manner, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality. Agriculturally useful salts of the compounds of formula I encompass especially the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the mode of action of the compounds of formula I. Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydro- gensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can preferably be formed by reacting compounds of formula I with an acid of the corresponding anion, preferably of hydrochlo- ric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
In certain embodiments, the present invention relates to agricultural mixtures as defined herein comprising at least one of the compounds as defined in any one of the embodiments from first embodiment to the forty nineth embodiment. Further, in certain other embodiments, the pre- sent invention relates to compositions as defined herein comprising at least one of the any one of the embodiments from first embodiment to the forty nineth embodiments.
In certain other embodiments, the present invention relates to the methods as defined herein comprising the application of any one of the compounds as defined in any one of the embodiments any one of the embodiments from first embodiment to the forty nineth embodiment The compounds of the formula (I) or compositions comprising said compounds according to the invention and the mixtures comprising said compounds and compositions, respectively, are suitable as agrochemical fungicides.
They are distinguished by an outstanding effectiveness against a broad spectrum of phytopatho- genic fungi, which derive especially from the following classes or are closely related to any of them: Solani, for example, but not limited to the genus Alternaria; fusarium or Rhizoctonia; Soro- kiniana, for example, but not limited to the genus Bipolaris; Cinerea, for example, not limited to Botyris; Miyabeanus, not limited to Cochliobolus; Orbiculare, not limited to Colletotrichum; Teres, but not limited to Drechslera or Pyrenophora ; Repentis, but not limited to Tritici; Erysiphe spp. ; Culmorum, but not limited to Fusarium; Nivale, but not limited to Microdochium; Monilinia spp. e. g. M. laxa, M. fructicola and M. fructigena; Oryzae, but not limited to Bipolaris, Entyloma, Hem- ileia, Pyricularia and Rocladium; Pachyrhizi, but not limited to Phakopspora; Sclerotiorium, but not limited to Sclerotinia; Tritici, but not limited to Zymoseptoria; Basicola, but not limited to Thielaviopsis; Maydis, but not limited to Ustilago.
The compounds of formula (I) further show phytopathogenic activity against pathogens that are resistant to complex 2 or complex 3 respiratory chain inhibitors e.g: in Sclerotinia sclerotiorum and/or Botyris cinerea.
Some of the compounds of the formula I and the compositions according to the invention are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
The compounds I and the compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g. apples, pears, plums, peaches, almonds, cherries, straw- berries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, toma- toes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, sugar cane or oil palm; corn; to- bacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e. g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants.
Preferably, compounds I and compositions thereof, respectively are used for controlling a multi- tude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamen- tals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pour ing.
Preferably, treatment of plant propagation materials with compounds I and compositions thereof, respectively, is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
The term "cultivated plants" is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://cera-gmc.org/, see GM crop database therein). Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be ob- tained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by glycosylation or poly- mer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
Plants that have been modified by breeding, mutagenesis or genetic engineering, e. g. have been rendered tolerant to applications of specific classes of herbicides, such as auxin herbicides such as dicamba or 2,4-D; bleacher herbicides such as hydroxylphenylpyruvate dioxygenase (HPPD) inhibitors or phytoene desaturase (PDS) inhibitors; acetolactate synthase (ALS) inhibitors such as sulfonyl ureas or imidazolinones; enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhib- itors, such as glyphosate; glutamine synthetase (GS) inhibitors such as glufosinate; protoporphy- rinogen-IX oxidase inhibitors; lipid biosynthesis inhibitors such as acetyl CoA carboxylase (AC- Case) inhibitors; or oxynil (i. e. bromoxynil or ioxynil) herbicides as a result of conventional meth- ods of breeding or genetic engineering. Furthermore, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glypho- sate and glufosinate or to both glyphosate and a herbicide from another class such as ALS inhib- itors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors. These herbicide resistance tech- nologies are e. g. described in Pest Managem. Sci.61, 2005, 246; 61, 2005, 258; 61, 2005, 277; 61, 2005, 269; 61, 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Sci.57, 2009, 108; Austral. J. Agricult. Res.58, 2007, 708; Science 316, 2007, 1185; and references quoted therein. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), e. g. Clearfield® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g. imazamox, or ExpressSun® sunflowers (DuPont, USA) being tolerant to sul- fonyl ureas, e. g. tribenuron. Genetic engineering methods have been used to render cultivated plants such as soybean, cotton, corn, beets and rape, tolerant to herbicides such as glyphosate and glufosinate, some of which are commercially available under the trade names Round- upReady® (glyphosate-tolerant, Monsanto, U.S.A.), Cultivance® (imidazolinone tolerant, BASF SE, Germany) and LibertyLink® (glufosinate-tolerant, Bayer CropScience, Germany).
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as δ-endotoxins, e. g. CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1, VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibi- tors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-trans- ferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilbene synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, e. g. WO 02/015701). Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, e. g., in EP-A 374753, WO 93/007278, WO 95/34656, EP-A 427529, EP-A 451878, WO 03/18810 und WO 03/52073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of arthropods, especially to beetles (Coeloptera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda). Genetically modified plants capable to synthesize one or more insecticidal proteins are, e. g., described in the publications mentioned above, and some of which are commercially available such as YieldGard® (corn cultivars producing the Cry1Ab toxin), YieldGard® Plus (corn cultivars producing Cry1Ab and Cry3Bb1 toxins), Starlink® (corn cultivars producing the Cry9c toxin), Herculex® RW (corn cultivars producing Cry34Ab1, Cry35Ab1 and the enzyme phosphinothricin-N-acetyltransferase [PAT]); NuCOTN® 33B (cotton cultivars producing the Cry1Ac toxin), Bollgard® I (cotton cultivars producing the Cry1Ac toxin), Bollgard® II (cotton cultivars producing Cry1Ac and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing a VIP-toxin); NewLeaf® (potato cultivars producing the Cry3A toxin); Bt-Xtra®, Nature- Gard®, KnockOut®, BiteGard®, Protecta®, Bt11 (e. g. Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivars producing the Cry1Ab toxin and PAT enyzme), MIR604 from Syngenta Seeds SAS, France (corn cultivars producing a modified version of the Cry3A toxin, c.f. WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a mod- ified version of the Cry1Ac toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1F toxin and PAT enzyme).
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bac- terial, viral or fungal pathogens. Examples of such proteins are the so-called“pathogenesis-re- lated proteins” (PR proteins, see, e. g. EP-A 392225), plant disease resistance genes (e. g. po- tato cultivars, which express resistance genes acting against Phytophthora infestans derived from the Mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amyl- vora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above.
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth- limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g. oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera® rape, DOW Agro Sciences, Canada). Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Am- flora® potato, BASF SE, Germany).
The compounds of formula (I) and compositions thereof, respectively, are particularly suitable for controlling the following plant diseases:
Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. candida) and sunflowers (e. g. A. tragopogonis); Alternaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassicola or brassi- cae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A. alternata), to- matoes (e. g. A. solani or A. alternata) and wheat; Aphanomyces spp. on sugar beets and vege- tables; Ascochyta spp. on cereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A. hordei on barley; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on corn, e. g. spot blotch (B. sorokiniana) on cereals and e. g. B. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn (e. g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice; Cladosporium spp. on tomatoes (e. g. C. fulvum: leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helminthosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C. miyabeanus, anamorph: H. oryzae); Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e. g. C. graminicola: Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemuthianum) and soybeans (e. g. C. truncatum or C. gloeosporioides); Corticium spp., e. g. C. sasakii (sheath blight) on rice; Corynespora cas- siicola (leaf spots) on soybeans and ornamentals; Cycloconium spp., e. g. C. oleaginum on olive trees; Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C. liriodendri, teleomorph: Neonectria liriodendri: Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeo moniella chlamydospora (earlier Phaeoacremonium chlamydosporum), Phaeoacremonium ale- ophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta: anthracnose) and vines (E. ampelina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoc- cum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (E. betae), vegetables (e. g. E. pisi), such as cucurbits (e. g. E. cichoracearum), cabbages, rape (e. g. E. cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e. g. E. turcicum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on var- ious plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. solani (f. sp. glycines now syn. F. virguli- forme ) and F. tucumaniae and F. brasiliense each causing sudden death syndrome on soybeans, and F. verticillioides on corn; Gaeumannomyces graminis (take-all) on cereals (e. g. wheat or barley) and corn; Gibberella spp. on cereals (e. g. G. zeae) and rice (e. g. G. fujikuroi: Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grainstaining complex on rice; Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macropho- mina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (pow- dery mildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas; Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae), rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco (P. tabacina) and soybeans (e. g. P. manshurica); Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tra- cheiphila and P. tetraspora) and soybeans (e. g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e. g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans: late blight) and broad-leaved trees (e. g. P. ramorum: sudden oak death); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants; Plasmo- para spp., e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits, e. g. P. leu- cotricha on apples; Polymyxa spp., e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and thereby transmitted viral diseases; Pseudocercosporella herpotrich- oides (eyespot, teleomorph: Tapesia yallundae) on cereals, e. g. wheat or barley; Pseudoperono- spora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. humili on hop; Pseu- dopezicula tracheiphila (red fire disease or‚rotbrenner’, anamorph: Phialophora) on vines; Puc- cinia spp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P. asparagi on asparagus; Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum); Ramularia spp., e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis (scald) on bar- ley, rye and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e. g. S. sclero- tiorum) and soybeans (e. g. S. rolfsii or S. sclerotiorum); Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagono- spora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines; Setospaeria spp. (leaf blight) on corn (e. g. S. turci- cum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. S. reili- ana: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucur- bits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral dis- eases; Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Lep- tosphaeria [syn. Phaeosphaeria] nodorum) on wheat; Synchytrium endobioticum on potatoes (po- tato wart disease); Taphrina spp., e. g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stink- ing smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e. g. U. appen- diculatus, syn. U. phaseoli) and sugar beets (e. g. U. betae); Ustilago spp. (loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab) on apples (e. g. V. inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae on strawberries, rape, potatoes and tomatoes.
In a preferred embodiment the compounds I and compositions thereof, respectively, are particu- larly suitable for controlling the following plant diseases: Puccinia spp. (rusts) on various plants, for example, but not limited to P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye and Phakopsoraceae spp. on various plants, in partic- ular Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans.
The compounds I and compositions thereof, respectively, are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials.
The term "protection of materials" is to be understood to denote the protection of technical and non-living materials, such as adhesives, glues, wood, paper and paperboard, textiles, leather, paint dispersions, plastics, cooling lubricants, fiber or fabrics, against the infestation and destruc tion by harmful microorganisms, such as fungi and bacteria. As to the protection of wood and other materials, the particular attention is paid to the following harmful fungi: Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaeto- mium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., and in addition in the protection of stored products and harvest the following yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.
The method of treatment according to the invention can also be used in the field of protecting stored products or harvest against attack of fungi and microorganisms. According to the present invention, the term "stored products" is understood to denote natural substances of plant or animal origin and their processed forms, which have been taken from the natural life cycle and for which long-term protection is desired. Stored products of crop plant origin, such as plants or parts thereof, for example stalks, leafs, tubers, seeds, fruits or grains, can be protected in the freshly harvested state or in processed form, such as pre-dried, moistened, comminuted, ground, pressed or roasted, which process is also known as post-harvest treatment. Also falling under the definition of stored products is timber, whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood. Stored products of animal origin are hides, leather, furs, hairs and the like. The combinations according the present invention can prevent disadvantageous effects such as de- cay, discoloration or mold. Preferably "stored products" is understood to denote natural sub- stances of plant origin and their processed forms, more preferably fruits and their processed forms, such as pomes, stone fruits, soft fruits and citrus fruits and their processed forms.
The compounds of formula I can be present in different crystal modifications whose biological activity may differ. They are likewise subject matter of the present invention.
The compounds I are employed as such or in form of compositions by treating the fungi or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be pro- tected from fungal attack with a fungicidally effective amount of the active substances. The appli- cation can be carried out both before and after the infection of the plants, plant propagation ma- terials, such as seeds, soil, surfaces, materials or rooms by the fungi.
Plant propagation materials may be treated with compounds I as such or a composition compris- ing at least one compound I prophylactically either at or before planting or transplanting.
The invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I according to the invention.
An agrochemical composition comprises a fungicidally effective amount of a compound I. The term "effective amount" denotes an amount of the composition or of the compounds I, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound I used. The compounds (I), their N-oxides and salts can be converted into customary types of agrochem- ical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e. g. SC, OD, FS), emulsifiable concentrates (e. g. EC), emulsions (e. g. EW, EO, ES, ME), capsules (e. g. CS, ZC), pastes, pastilles, wettable powders or dusts (e. g. WP, SP, WS, DP, DS), pressings (e. g. BR, TB, DT), granules (e. g. WG, SG, GR, FG, GG, MG), insecticidal articles (e. g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e. g. GF). These and further compositions types are defined in the“Catalogue of pesticide formulation types and international coding system”, Technical Monograph No.2, 6th Ed. May 2008, CropLife Inter- national.
The compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bac- tericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e. g. kerosene, diesel oil; oils of vegetable or animal origin; ali- phatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e. g. ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, e. g. cyclohexanone; esters, e. g. lactates, carbonates, fatty acid esters, gamma- butyrolactone; fatty acids; phosphonates; amines; amides, e. g. N-methyl pyrrolidone, fatty acid dimethyl amides; and mixtures thereof.
Suitable solid carriers or fillers are mineral earths, e. g. silicates, silica gels, talc, kaolins, lime- stone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e. g. cellulose, starch; fertilizers, e. g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e. g. ce- real meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and am- photeric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon’s, Vol.1: Emulsifiers & Detergents, McCutcheon’s Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.). Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of con- densed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkyl naphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, es- ters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkox- ylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N- substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfac- tants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinyl pyrrolidone, vinyl alcohols, or vinyl acetate.
Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium com- pounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable am- photeric surfactants are alkylbetains and imidazolines. Suitable block polymers are block poly- mers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinyl amines or polyethylene amines.
Suitable adjuvants are compounds, which have a negligible or even no pesticidal activity them- selves, and which improve the biological performance of the compound I on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5. Suitable thickeners are polysaccharides (e. g. xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
Suitable colorants (e. g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e. g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e. g. alizarin-, azo- and phthalocyanine colorants).
Suitable tackifiers or binders are polyvinyl pyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers. Examples for composition types and their preparation are:
i) Water-soluble concentrates (SL, LS)
10-60 wt% of a compound I and 5-15 wt% wetting agent (e. g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e. g. alcohols) ad 100 wt%. The active substance dissolves upon dilution with water.
ii) Dispersible concentrates (DC)
5-25 wt% of a compound I and 1-10 wt% dispersant (e. g. polyvinyl pyrrolidone) are dissolved in organic solvent (e. g. cyclohexanone) ad 100 wt%. Dilution with water gives a dispersion.
iii) Emulsifiable concentrates (EC)
15-70 wt% of a compound I and 5-10 wt% emulsifiers (e. g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in water-insoluble organic solvent (e. g. aromatic hydro- carbon) ad 100 wt%. Dilution with water gives an emulsion.
iv) Emulsions (EW, EO, ES) 540 wt% of a compound I and 110 wt% emulsifiers (e. g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% water-insoluble organic solvent (e. g. aromatic hydrocarbon). This mixture is introduced into water ad 100 wt% by means of an emulsifying ma- chine and made into a homogeneous emulsion. Dilution with water gives an emulsion.
v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20-60 wt% of a compound I are comminuted with addition of 2-10 wt% dispersants and wetting agents (e. g. sodium lignosulfonate and alcohol ethoxylate), 0.1-2 wt% thickener (e. g. xanthan gum) and water ad 100 wt% to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt% binder (e. g. polyvinyl alcohol) is added.
vi) Water-dispersible granules and water-soluble granules (WG, SG)
50-80 wt% of a compound I are ground finely with addition of dispersants and wetting agents (e. g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt% and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)
50-80 wt% of a compound I are ground in a rotor-stator mill with addition of 1-5 wt% dispersants (e. g. sodium lignosulfonate), 1-3 wt% wetting agents (e. g. alcohol ethoxylate) and solid carrier (e. g. silica gel) ad 100 wt%. Dilution with water gives a stable dispersion or solution of the active substance.
viii) Gel (GW, GF)
In an agitated ball mill, 5-25 wt% of a compound I are comminuted with addition of 3-10 wt% dispersants (e. g. sodium lignosulfonate), 1-5 wt% thickener (e. g. carboxymethyl cellulose) and water ad 100 wt% to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
ix) Microemulsion (ME)
5-20 wt% of a compound I are added to 5-30 wt% organic solvent blend (e. g. fatty acid dimethyl amide and cyclohexanone), 10-25 wt% surfactant blend (e. g. alcohol ethoxylate and arylphenol ethoxylate), and water ad 100 %. This mixture is stirred for 1 h to produce spontaneously a ther- modynamically stable microemulsion.
x) Microcapsules (CS)
An oil phase comprising 5-50 wt% of a compound I, 0-40 wt% water insoluble organic solvent (e. g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e. g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e. g. poly- vinyl alcohol). Radical polymerization results in the formation of poly(meth)acrylate microcap- sules. Alternatively, an oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e. g. aromatic hydrocarbon), and an isocyanate mon- omer (e. g. diphenylmethene-4,4’-diisocyanatae) are dispersed into an aqueous solution of a pro- tective colloid (e. g. polyvinyl alcohol). The addition of a polyamine (e. g. hexamethylenediamine) results in the formation of polyurea microcapsules. The monomers amount to 1-10 wt%. The wt% relate to the total CS composition.
xi) Dustable powders (DP, DS)
1-10 wt% of a compound I are ground finely and mixed intimately with solid carrier (e. g. finely divided kaolin) ad 100 wt%. xii) Granules (GR, FG)
0.5-30 wt% of a compound I is ground finely and associated with solid carrier (e. g. silicate) ad 100 wt%. Granulation is achieved by extrusion, spray-drying or fluidized bed.
xiii) Ultra-low volume liquids (UL)
1-50 wt% of a compound I are dissolved in organic solvent (e. g. aromatic hydrocarbon) ad 100 wt%.
The compositions types i) to xiii) may optionally comprise further auxiliaries, such as 0.1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1-1 wt% anti-foaming agents, and 0.1-1 wt% col- orants. The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, more preferably between 1 and 70%, and in particular between 10 and 60%, by weight of active substance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
For the purposes of treatment of plant propagation materials, particularly seeds, solutions for seed treatment (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emul- sions (ES), emulsifiable concentrates (EC), and gels (GF) are usually employed. The composi- tions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying compound I and compositions thereof, respectively, onto plant propagation material, especially seeds, include dressing, coating, pelleting, dusting, and soaking as well as in-furrow application methods. Preferably, compound I or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dust- ing. When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.
In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propa- gation material (preferably seeds) are generally required.
When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides (e. g. herbicides, insecticides, fungicides, growth regulators, safeners, biopesticides) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions accord- ing to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1. A pesticide is generally a chemical or biological agent (such as pestidal active ingredient, com pound, composition, virus, bacterium, antimicrobial or disinfectant) that through its effect deters, incapacitates, kills or otherwise discourages pests. Target pests can include insects, plant path- ogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microbes that de- stroy property, cause nuisance, spread disease or are vectors for disease. The term“pesticide” includes also plant growth regulators that alter the expected growth, flowering, or reproduction rate of plants; defoliants that cause leaves or other foliage to drop from a plant, usually to facilitate harvest; desiccants that promote drying of living tissues, such as unwanted plant tops; plant acti- vators that activate plant physiology for defense of against certain pests; safeners that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology e.g. to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.
The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to- use spray liquor are applied per hectare of agricultural useful area.
According to one embodiment, individual components of the composition according to the inven- tion such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate. Consequently, one embodiment of the invention is a kit for preparing a usable pesticidal compo- sition, the kit comprising a) a composition comprising component 1) as defined herein and at least one auxiliary; and b) a composition comprising component 2) as defined herein and at least one auxiliary; and optionally c) a composition comprising at least one auxiliary and optionally a further active component 3) as defined herein.
Mixing the compounds (I) or the compositions comprising them in the use form as fungicides with other fungicides results in many cases in an expansion of the fungicidal spectrum of activity being obtained or in a prevention of fungicide resistance development. Furthermore, in many cases, synergistic effects are obtained.
The following list of pesticides II (e. g. pesticidally-active substances and biopesticides), in con- junction with which the compounds I can be used, is intended to illustrate the possible combina- tions but does not limit them:
A) Respiration inhibitors: Inhibitors of complex III at Qo site: azoxystrobin (A.1.1), coumeth- oxystrobin (A.1.2), coumoxystrobin (A.1.3), dimoxystrobin (A.1.4), enestroburin (A.1.5), fenamin- strobin (A.1.6), fenoxystrobin/flufenoxystrobin (A.1.7), fluoxastrobin (A.1.8), kresoxim-methyl (A.1.9), mandestrobin (A.1.10), metominostrobin (A.1.11), orysastrobin (A.1.12), picoxystrobin (A.1.13), pyraclostrobin (A.1.14), pyrametostrobin (A.1.15), pyraoxystrobin (A.1.16), trifloxy- strobin (A.1.17), 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)- 2-methoxyimino-N-methyl-acetamide (A.1.18), pyribencarb (A.1.19), triclopyricarb/chlorodincarb (A.1.20), famoxadone (A.1.21), fenamidone (A.1.21), methyl-N-[2-[(1,4-dimethyl-5-phenyl-pyra- zol-3-yl)oxylmethyl]phenyl]-N-methoxy-carbamate (A.1.22), 1-[3-chloro-2-[[1-(4-chlorophenyl)- 1H pyrazol 3 yl]oxymethyl]phenyl] 4 methyl tetrazol 5 one (A.1.23), 1 [3 bromo 2 [[1 (4 chloro phenyl)pyrazol-3-yl]oxymethyl]phenyl]-4-methyl-tetrazol-5-one (A.1.24), 1-[2-[[1-(4-chloro- phenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one (A.1.25), 1-[2-[[1-(4- chlorophenyl)pyrazol-3-yl]oxymethyl]-3-fluoro-phenyl]-4-methyl-tetrazol-5-one (A.1.26), 1-[2-[[1- (2,4-dichlorophenyl)pyrazol-3-yl]oxymethyl]-3-fluoro-phenyl]-4-methyl-tetrazol-5-one (A.1.27), 1- [2-[[4-(4-chlorophenyl)thiazol-2-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one (A.1.28), 1-[3-chloro-2-[[4-(p-tolyl)thiazol-2-yl]oxymethyl]phenyl]-4-methyl-tetrazol-5-one (A.1.29), 1-[3-cy- clopropyl-2-[[2-methyl-4-(1-methylpyrazol-3-yl)phenoxy]methyl]phenyl]-4-methyl-tetrazol-5-one (A.1.30), 1-[3-(difluoromethoxy)-2-[[2-methyl-4-(1-methylpyrazol-3-yl)phenoxy]methyl]phenyl]- 4-methyl-tetrazol-5-one (A.1.31), 1-methyl-4-[3-methyl-2-[[2-methyl-4-(1-methylpyrazol-3-yl)phe- noxy]methyl]phenyl]tetrazol-5-one (A.1.32), 1-methyl-4-[3-methyl-2-[[1-[3-(trifluoromethyl)phe- nyl]-ethylideneamino]oxymethyl]phenyl]tetrazol-5-one (A.1.33), (Z,2E)-5-[1-(2,4-dichloro- phenyl)pyrazol-3-yl]­oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (A.1.34), (Z,2E)-5-[1-(4- chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (A.1.35), pyrim- inostrobin (A.1.36), bifujunzhi (A.1.37), 2-(ortho-((2,5-dimethylphenyl-oxymethylen)phenyl)-3- methoxy-acrylic acid methylester (A.1.38).
Inhibitors of complex III at Qi site: cyazofamid (A.2.1), amisulbrom (A.2.2), [(6S,7R,8R)-8-benzyl- 3-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] 2- methylpropanoate (A.2.3), [2-[[(7R,8R,9S)-7-benzyl-9-methyl-8-(2-methylpropanoyloxy)-2,6-di- oxo-1,5-dioxonan-3-yl]carbamoyl]-4-methoxy-3-pyridyl]oxymethyl 2-methylpropanoate (A.2.4), [(6S,7R,8R)-8-benzyl-3-[[4-methoxy-3-(propanoyloxymethoxy)pyridine-2-carbonyl]amino]-6-me- thyl-4,9-dioxo-1,5-dioxonan-7-yl] 2-methylpropanoate (A.2.5).
Inhibitors of complex II: benodanil (A.3.1), benzovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapyroxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.11), isopyrazam (A.3.12), mepronil (A.3.13), oxycar- boxin (A.3.14), penflufen (A.3.15), penthiopyrad (A.3.16), 3-(difluoromethyl)-N-methoxy-1-methyl- N-[1-methyl-2-(2,4,6-trichlorophenyl)ethyl]pyrazole-4-carboxamide (A.3.17), N-[2-(3,4-difluoro- phenyl)phenyl]-3-(trifluoromethyl)pyrazine-2-carboxamide (A.3.18), sedaxane (A.3.19), te- cloftalam (A.3.20), thifluzamide (A.3.21), 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethylindan-4- yl)pyrazole-4-carboxamide (A.3.22), 3-(trifluoromethyl)-1-methyl-N-(1,1,3-trimethylindan-4-yl)py- razole-4-carboxamide (A.3.23), 1,3-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carbox- amide (A.3.24), 3-(trifluoromethyl)-1,5-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carbox- amide (A.3.25), 1,3,5-trimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.26), 3- (difluoromethyl)-1,5-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.27), 3- (difluoromethyl)-N-(7-fluoro-1,1,3-trimethyl-indan-4-yl)-1-methyl-pyrazole-4-carboxamide (A.3.28), methyl (E)-2-[2-[(5-cyano-2-methyl-phenoxy)methyl]phenyl]-3-methoxy-prop-2-enoate (A.3.30), N-[(5-chloro-2-isopropyl-phenyl)methyl]-N-cyclopropyl-3-(difluoromethyl)-5 fluoro-1-me- thyl-pyrazole-4-carboxamide (A.3.31), 2-(difluoromethyl)-N-(1,1,3-trimethyl-indan-4-yl)pyridine-3- carboxamide (A.3.32), 2-(difluoromethyl)-N-[(3R)-1,1,3-trimethylindan-4-yl]pyridine-3-carbox- amide (A.3.33), 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)¬pyridine-3-carboxamide (A.3.34), 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]¬pyridine-3-carboxamide (A.3.35), 2-(difluoromethyl)-N-(1,1-dimethyl-3-propyl-indan-4-yl)¬py¬ridine-3-carboxamide (A.3.36), 2-(difluoromethyl)-N-[(3R)-1,1-dimethyl-3-propyl-indan-4-yl]¬pyridine-3-carboxamide (A.3.37), 2-(difluoromethyl)-N-(3-isobutyl-1,1-dimethyl-indan-4-yl)¬pyridine-3-carboxamide (A.3.38), 2 (difluoromethyl) N [(3R) 3 isobutyl 1,1 dimethyl indan 4 yl]pyridine 3 carboxamide (A.3.39).
Other respiration inhibitors: diflumetorim (A.4.1); nitrophenyl derivates: binapacryl (A.4.2), dino- buton (A.4.3), dinocap (A.4.4), fluazinam (A.4.5), meptyldinocap (A.4.6), ferimzone (A.4.7); or- ganometal compounds: fentin salts, e. g. fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.11); silthiofam (A.4.12).
B) Sterol biosynthesis inhibitors (SBI fungicides)
C14 demethylase inhibitors: triazoles: azaconazole (B.1.1), bitertanol (B.1.2), bromuconazole (B.1.3), cyproconazole (B.1.4), difenoconazole (B.1.5), diniconazole (B.1.6), diniconazole-M (B.1.7), epoxiconazole (B.1.8), fenbuconazole (B.1.9), fluquinconazole (B.1.10), flusilazole (B.1.11), flutriafol (B.1.12), hexaconazole (B.1.13), imibenconazole (B.1.14), ipconazole (B.1.15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1.19), paclobutrazole (B.1.20), penconazole (B.1.21), propiconazole (B.1.22), prothioconazole (B.1.23), simeconazole (B.1.24), tebuconazole (B.1.25), tetraconazole (B.1.26), triadimefon (B.1.27), triadimenol (B.1.28), triticon- azole (B.1.29), uniconazole (B.1.30), 1-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)- oxiranylmethyl]-5-thiocyanato-1H-[1,2,4]triazole (B.1.31), 2-[rel-(2S;3R)-3-(2-chlorophenyl)-2- (2,4-difluorophenyl)-oxiranylmethyl]-2H-[1,2,4]triazole-3-thiol (B.1.32), 2-[2-chloro-4-(4-chloro- phenoxy)phenyl]-1-(1,2,4-triazol-1-yl)pentan-2-ol (B.1.33), 1-[4-(4-chlorophenoxy)-2-(trifluorome- thyl)phenyl]-1-cyclopropyl-2-(1,2,4-triazol-1-yl)ethanol (B.1.34), 2-[4-(4-chlorophenoxy)-2-(trifluo- romethyl)phenyl]-1-(1,2,4-triazol-1-yl)butan-2-ol (B.1.35), 2-[2-chloro-4-(4-chlorophenoxy)phe- nyl]-1-(1,2,4-triazol-1-yl)butan-2-ol (B.1.36), 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]- 3-methyl-1-(1,2,4-triazol-1-yl)butan-2-ol (B.1.37), 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phe- nyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (B.1.38), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-3-methyl- 1-(1,2,4-triazol-1-yl)butan-2-ol (B.1.39), 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1- (1,2,4-triazol-1-yl)pentan-2-ol (B.1.40), 2-[4-(4-fluorophenoxy)-2-(trifluoromethyl)phenyl]-1- (1,2,4-triazol-1-yl)propan-2-ol (B.1.41), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1,2,4-triazol-1- yl)pent-3-yn-2-ol (B.1.42), 2-(chloromethyl)-2-methyl-5-(p-tolylmethyl)-1-(1,2,4-triazol-1-ylme- thyl)cyclopentanol (B.1.43); imidazoles: imazalil (B.1.44), pefurazoate (B.1.45), prochloraz (B.1.46), triflumizol (B.1.47); pyrimidines, pyridines and piperazines: fenarimol (B.1.49), pyrifenox (B.1.50), triforine (B.1.51), [3-(4-chloro-2-fluoro-phenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]-(3- pyridyl)methanol (B.1.52).
Delta14-reductase inhibitors: aldimorph (B.2.1), dodemorph (B.2.2), dodemorph-acetate (B.2.3), fenpropimorph (B.2.4), tridemorph (B.2.5), fenpropidin (B.2.6), piperalin (B.2.7), spiroxamine (B.2.8).
Inhibitors of 3-keto reductase: fenhexamid (B.3.1).
Other Sterol biosynthesis inhibitors: chlorphenomizole (B.4.1).
C) Nucleic acid synthesis inhibitors
Phenylamides or acyl amino acid fungicides: benalaxyl (C.1.1), benalaxyl-M (C.1.2), kiralaxyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (C.1.5), ofurace (C.1.6), oxadixyl (C.1.7).
Other nucleic acid synthesis inhibitors: hymexazole (C.2.1), octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine (C.2.6), 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine (C.2.7), 5-fluoro-2-(4-chlorophenyl- methoxy)pyrimidin-4 amine (C.2.8).
D) Inhibitors of cell division and cytoskeleton Tubulin inhibitors: benomyl (D.1.1), carbendazim (D.1.2), fuberidazole (D1.3), thiabendazole (D.1.4), thiophanate-methyl (D.1.5), 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine (D.1.6), 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine (D.1.7), N-ethyl-2-[(3- ethynyl-8-methyl-6-quinolyl)oxy]butanamide (D.1.8), N-ethyl-2-[(3-ethynyl-8-methyl- 6-quinolyl)oxy]-2-methylsulfanyl-acetamide (D.1.9), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-(2- fluoroethyl)butanamide (D.1.10), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-(2-fluoroethyl)-2-meth- oxy-acetamide (D.1.11), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-propyl-butanamide (D.1.12), 2- [(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methoxy-N-propyl-acetamide (D.1.13), 2-[(3-ethynyl-8-me- thyl-6-quinolyl)oxy]-2-methylsulfanyl-N-propyl-acetamide (D.1.14), 2-[(3-ethynyl-8-methyl-6- quinolyl)oxy]-N-(2-fluoroethyl)-2-methylsulfanyl-acetamide (D.1.15), 4-(2-bromo-4-fluoro-phe- nyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine (D.1.16).
Other cell division inhibitors: diethofencarb (D.2.1), ethaboxam (D.2.2), pencycuron (D.2.3), fluopicolide (D.2.4), zoxamide (D.2.5), metrafenone (D.2.6), pyriofenone (D.2.7).
E) Inhibitors of amino acid and protein synthesis
Methionine synthesis inhibitors: cyprodinil (E.1.1), mepanipyrim (E.1.2), pyrimethanil (E.1.3). Protein synthesis inhibitors: blasticidin-S (E.2.1), kasugamycin (E.2.2), kasugamycin hydrochlo- ride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6).
F) Signal transduction inhibitors
MAP / histidine kinase inhibitors: fluoroimid (F.1.1), iprodione (F.1.2), procymidone (F.1.3), vin- clozolin (F.1.4), fludioxonil (F.1.5).
G protein inhibitors: quinoxyfen (F.2.1).
G) Lipid and membrane synthesis inhibitors
Phospholipid biosynthesis inhibitors: edifenphos (G.1.1), iprobenfos (G.1.2), pyrazophos (G.1.3), isoprothiolane (G.1.4).
Lipid peroxidation: dicloran (G.2.1), quintozene (G.2.2), tecnazene (G.2.3), tolclofos-methyl (G.2.4), biphenyl (G.2.5), chloroneb (G.2.6), etridiazole (G.2.7).
Phospholipid biosynthesis and cell wall deposition: dimethomorph (G.3.1), flumorph (G.3.2), man- dipropamid (G.3.3), pyrimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7).
Compounds affecting cell membrane permeability and fatty acides: propamocarb (G.4.1).
Inhibitors of oxysterol binding protein: oxathiapiprolin (G.5.1), 2-{3-[2-(1-{[3,5-bis(difluoromethyl- 1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}phenyl me- thanesulfonate (G.5.2), 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl) 1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate (G.5.3), 4-[1-[2- [3-(difluoromethyl)-5-methyl-pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carbox- amide (G.5.4), 4-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyri- dine-2-carboxamide (G.5.5), 4-[1-[2-[3-(difluoromethyl)-5-(trifluoromethyl)pyrazol-1-yl]acetyl]-4- piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.6), 4-[1-[2-[5-cyclopropyl-3-(difluorome- thyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.7), 4-[1-[2-[5-me- thyl-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.8), 4-[1-[2-[5-(difluoromethyl)-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1- yl-pyridine-2-carboxamide (G.5.9), 4-[1-[2-[3,5-bis(trifluoromethyl)pyrazol-1-yl]acetyl]-4-pi- peridyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.10), (4-[1-[2-[5-cyclopropyl-3-(trifluorome- thyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.11). H) Inhibitors with Multi Site Action
Inorganic active substances: Bordeaux mixture (H.1.1), copper (H.1.2), copper acetate (H.1.3), copper hydroxide (H.1.4), copper oxychloride (H.1.5), basic copper sulfate (H.1.6), sulfur (H.1.7). Thio- and dithiocarbamates: ferbam (H.2.1), mancozeb (H.2.2), maneb (H.2.3), metam (H.2.4), metiram (H.2.5), propineb (H.2.6), thiram (H.2.7), zineb (H.2.8), ziram (H.2.9).
Organochlorine compounds: anilazine (H.3.1), chlorothalonil (H.3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorphenole (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.11).
Guanidines and others: guanidine (H.4.1), dodine (H.4.2), dodine free base (H.4.3), guazatine (H.4.4), guazatine-acetate (H.4.5), iminoctadine (H.4.6), iminoctadine-triacetate (H.4.7), iminoctadine-tris(albesilate) (H.4.8), dithianon (H.4.9), 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6- c']dipyrrole-1,3,5,7(2H,6H)-tetraone (H.4.10).
I) Cell wall synthesis inhibitors
Inhibitors of glucan synthesis: validamycin (I.1.1), polyoxin B (I.1.2).
Melanin synthesis inhibitors: pyroquilon (I.2.1), tricyclazole (I.2.2), carpropamid (I.2.3), dicyclomet (I.2.4), fenoxanil (I.2.5).
J) Plant defence inducers
Acibenzolar-S-methyl (J.1.1), probenazole (J.1.2), isotianil (J.1.3), tiadinil (J.1.4), prohexadione- calcium (J.1.5); phosphonates: fosetyl (J.1.6), fosetyl-aluminum (J.1.7), phosphorous acid and its salts (J.1.8), potassium or sodium bicarbonate (J.1.9), 4-cyclopropyl-N-(2,4-dimethoxyphenyl)thi- adiazole-5-carboxamide (J.1.10).
K) Unknown mode of action
Bronopol (K.1.1), chinomethionat (K.1.2), cyflufenamid (K.1.3), cymoxanil (K.1.4), dazomet (K.1.5), debacarb (K.1.6), diclocymet (K.1.7), diclomezine (K.1.8), difenzoquat (K.1.9), difen- zoquat-methylsulfate (K.1.10), diphenylamin (K.1.11), fenitropan (K.1.12), fenpyrazamine (K.1.13), flumetover (K.1.14), flusulfamide (K.1.15), flutianil (K.1.16), harpin (K.1.17), methasul- focarb (K.1.18), nitrapyrin (K.1.19), nitrothal-isopropyl (K.1.20), tolprocarb (K.1.21), oxin-copper (K.1.22), proquinazid (K.1.23), tebufloquin (K.1.24), tecloftalam (K.1.25), triazoxide (K.1.26), N'- (4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine (K.1.27), N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine (K.1.28), N'-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethyl- phenyl]-N-ethyl-N-methyl-formamidine (K.1.29), N'-(5-bromo-6-indan-2-yloxy-2-methyl-3- pyridyl)-N-ethyl-N-methyl-formamidine (K.1.30), N'-[5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2- methyl-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.31), N'-[5-bromo-6-(4-isopropylcyclo- hexoxy)-2-methyl-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.32), N'-[5-bromo-2-methyl-6-(1- phenylethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.33), N'-(2-methyl-5-trifluoromethyl- 4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine (K.1.34), N'-(5-difluorome- thyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine (K.1.35), 2-(4- chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide (K.1.36), 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (pyrisoxazole) (K.1.37), 3-[5-(4- methylphenyl)-2,3-dimethyl-isoxazolidin-3 yl]-pyridine (K.1.38), 5-chloro-1-(4,6-dimethoxy-pyrim- idin-2-yl)-2-methyl-1H-benzoimidazole (K.1.39), ethyl (Z)-3-amino-2-cyano-3-phenyl-prop-2-eno- ate (K.1.40), picarbutrazox (K.1.41), pentyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-meth- ylene]amino]oxymethyl]-2-pyridyl]carbamate (K.1.42), but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5- yl) phenyl methylene]amino]oxymethyl] 2 pyridyl]carbamate (K.1.43), 2 [2 [(7,8 difluoro 2 me thyl-3-quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol (K.1.44), 2-[2-fluoro-6-[(8-fluoro-2-methyl-3- quinolyl)oxy]phen-yl]propan-2-ol (K.1.45), 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin- 1-yl)quinoline (K.1.46), quinofumelin (K.1.47), 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquino- lin-1-yl)quinoline (K.1.48), 9-fluoro-2,2-dimethyl-5-(3-quinolyl)-3H-1,4-benzoxazepine (K.1.49), 2- (6-benzyl-2-pyridyl)quinazoline (K.1.50), 2-[6-(3-fluoro-4-methoxy-phenyl)-5-methyl-2- pyridyl]quinazoline (K.1.51), 3-[(3,4-dichloroisothiazol-5-yl)methoxy]-1,2-benzothiazole 1,1-diox- ide (K.1.52), N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine (K.1.53).
M) Growth regulators
abscisic acid (M.1.1), amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat, chlormequat chloride, choline chloride, cyclanilide, daminozide, dikegulac, dime- thipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibber- ellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat, mepiquat chloride, naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione, prohexadi- one-calcium, prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5-tri-io- dobenzoic acid , trinexapac-ethyl and uniconazole;
N) Herbicides from classes N.1 to N.15
N.1 Lipid biosynthesis inhibitors: alloxydim (N.1.1), alloxydim-sodium (N.1.2), butroxydim (N.1.3), clethodim (N.1.4), clodinafop (N.1.5), clodinafop-propargyl (N.1.6), cycloxydim (N.1.7), cyhalofop (N.1.8), cyhalofop-butyl (N.1.9), diclofop(N.1.10), diclofop-methyl (N.1.11), fenoxaprop (N.1.12), fenoxaprop-ethyl (N.1.13), fenoxaprop-P (N.1.14), fenoxaprop-P-ethyl (N.1.15), fluazifop (N.1.16), fluazifop-butyl (N.1.17), fluazifop-P (N.1.18), fluazifop-P-butyl (N.1.19), haloxyfop (N.1.20), haloxyfop-methyl (N.1.21), haloxyfop-P (N.1.22), haloxyfop-P-methyl (N.1.23), met- amifop (N.1.24), pinoxaden (N.1.25), profoxydim (N.1.26), propaquizafop (N.1.27), quizalofop (N.1.28), quizalofop-ethyl (N.1.29), quizalofop-tefuryl (N.1.30), quizalofop-P (N.1.31), quizalofop- P-ethyl (N.1.32), quizalofop-P-tefuryl (N.1.33), sethoxydim (N.1.34), tepraloxydim (N.1.35), tralkoxydim (N.1.36), 4-(4'-chloro-4-cyclo¬propyl-2'-fluoro[1,1'-biphenyl]-3-yl)-5-hydroxy-2,2,6,6- tetramethyl-2H-pyran-3(6H)-one ((N.1.37) CAS 1312337-72-6); 4-(2',4'-dichloro-4-cyclopro- pyl[1,1'-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one ((N.1.38) CAS 1312337-45-3); 4-(4'-chloro-4-ethyl-2'-fluoro[1,1'-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl- 2H-pyran-3(6H)-one ((N.1.39) CAS 1033757-93-5); 4-(2',4'-Dichloro-4-ethyl[1,1'-biphenyl]-3-yl)- 2,2,6,6-tetramethyl-2H-pyran-3,5(4H,6H)-dione ((N.1.40) CAS 1312340-84-3); 5-(acetyloxy)-4- (4'-chloro-4-cyclopropyl-2'-fluoro[1,1'-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3- one ((N.1.41) CAS 1312337-48-6); 5-(acetyloxy)-4-(2´,4'-dichloro-4-cyclopropyl- [1,1'-biphenyl]- 3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one (N.1.42); 5-(acetyloxy)-4-(4'-chloro-4-ethyl- 2'-fluoro[1,1'-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one ((N.1.43) CAS 1312340-82-1); 5-(acetyloxy)-4-(2',4'-dichloro-4-ethyl[1,1'-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tet- ramethyl-2H-pyran-3-one ((N.1.44) CAS 1033760-55-2); 4-(4'-chloro-4-cyclopropyl-2'-fluoro[1,1'- biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester ((N.1.45) CAS 1312337-51-1); 4-(2´,4'-dichloro -4-cyclopropyl- [1,1'-biphenyl]-3-yl)-5,6-dihydro- 2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester (N.1.46); 4-(4'-chloro-4-ethyl- 2'-fluoro[1,1'-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester ((N.1.47) CAS 1312340-83-2); 4-(2',4'-dichloro-4-ethyl¬[1,1'-biphenyl]-3-yl)-5,6-dihy- dro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester ((N.1.48) CAS 1033760- 585); benfuresate (N.1.49), butylate (N.1.50), cycloate (N.1.51), dalapon (N.1.52), dimepiperate (N.1.53), EPTC (N.1.54), esprocarb (N.1.55), ethofumesate (N.1.56), flupropanate (N.1.57), mo- linate (N.1.58), orbencarb (N.1.59), pebulate (N.1.60), prosulfocarb (N.1.61), TCA (N.1.62), thio- bencarb (N.1.63), tiocarbazil (N.1.64), triallate (N.1.65) and vernolate (N.1.66);
N.2 ALS inhibitors: amidosulfuron (N.2.1), azimsulfuron (N.2.2), bensulfuron (N.2.3), bensulfuron- methyl (N.2.4), chlorimuron (N.2.5), chlorimuron-ethyl (N.2.6), chlorsulfuron (N.2.7), cinosulfuron (N.2.8), cyclosulfamuron (N.2.9), ethametsulfuron (N.2.10), ethametsulfuron-methyl (N.2.11), eth- oxysulfuron (N.2.12), flazasulfuron (N.2.13), flucetosulfuron (N.2.14), flupyrsulfuron (N.2.15), flupyrsulfuron-methyl-sodium (N.2.16), foramsulfuron (N.2.17), halosulfuron (N.2.18), halosulfu- ron-methyl (N.2.19), imazosulfuron (N.2.20), iodosulfuron (N.2.21), iodosulfuron-methyl-sodium (N.2.22), iofensulfuron (N.2.23), iofensulfuron-sodium (N.2.24), mesosulfuron (N.2.25), met- azosulfuron (N.2.26), metsulfuron (N.2.27), metsulfuron-methyl (N.2.28), nicosulfuron (N.2.29), orthosulfamuron (N.2.30), oxasulfuron (N.2.31), primisulfuron (N.2.32), primisulfuron-methyl (N.2.33), propyrisulfuron (N.2.34), prosulfuron (N.2.35), pyrazosulfuron (N.2.36), pyrazosulfuron- ethyl (N.2.37), rimsulfuron (N.2.38), sulfometuron (N.2.39), sulfometuron-methyl (N.2.40), sul- fosulfuron (N.2.41), thifensulfuron (N.2.42), thifensulfuron-methyl (N.2.43), triasulfuron (N.2.44), tribenuron (N.2.45), tribenuron-methyl (N.2.46), trifloxysulfuron (N.2.47), triflusulfuron (N.2.48), triflusulfuron-methyl (N.2.49), tritosulfuron (N.2.50), imazamethabenz (N.2.51), imazamethabenz- methyl (N.2.52), imazamox (N.2.53), imazapic (N.2.54), imazapyr (N.2.55), imazaquin (N.2.56), imazethapyr (N.2.57); cloransulam (N.2.58), cloransulam-methyl (N.2.59), diclosulam (N.2.60), flumetsulam (N.2.61), florasulam (N.2.62), metosulam (N.2.63), penoxsulam (N.2.64), pyrimisul- fan (N.2.65) and pyroxsulam (N.2.66); bispyribac (N.2.67), bispyribac-sodium (N.2.68), pyriben- zoxim (N.2.69), pyriftalid (N.2.70), pyriminobac (N.2.71), pyriminobac-methyl (N.2.72), pyrithiobac (N.2.73), pyrithiobac-sodium (N.2.74), 4-[[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]me- thyl]amino]-benzoic acid-1-methyl¬ethyl ester ((N.2.75) CAS 420138-41-6), 4-[[[2-[(4,6-di- methoxy-2-pyrimidinyl)oxy]phenyl]¬methyl]amino]-benzoic acid propyl ester ((N.2.76) CAS 420138-40-5), N-(4-bromophenyl)-2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzenemethanamine ((N.2.77) CAS 420138-01-8); flucarbazone (N.2.78), flucarbazone-sodium (N.2.79), propoxy- carbazone (N.2.80), propoxycarbazone-sodium (N.2.81), thiencarbazone (N.2.82), thiencarba- zone-methyl (N.2.83), triafamone (N.2.84);
N.3 Photosynthesis inhibitors: amicarbazone (N.3.1); chlorotriazine (N.3.2); ametryn (N.3.3), at- razine (N.3.4), chloridazone (N.3.5), cyanazine (N.3.6), desmetryn (N.3.7), dimethametryn (N.3.8),hexazinone (N.3.9), metribuzin (N.3.10), prometon (N.3.11), prometryn (N.3.12), pro- pazine (N.3.13), simazine (N.3.14), simetryn (N.3.15), terbumeton (N.3.16), terbuthylazin (N.3.17), terbutryn (N.3.18), trietazin (N.3.19); chlorobromuron (N.3.20), chlorotoluron (N.3.21), chloroxuron (N.3.22), dimefuron (N.3.23), diuron (N.3.24), fluometuron (N.3.25), isoproturon (N.3.26), isouron (N.3.27), linuron (N.3.28), metamitron (N.3.29), methabenzthiazuron (N.3.30), metobenzuron (N.3.31), metoxuron (N.3.32), monolinuron (N.3.33), neburon (N.3.34), siduron (N.3.35), tebuthiuron (N.3.36), thiadiazuron (N.3.37), desmedipham (N.3.38), karbutilat (N.3.39), phenmedipham (N.3.40), phenmedipham-ethyl (N.3.41), bromofenoxim (N.3.42), bromoxynil (N.3.43) and its salts and esters, ioxynil (N.3.44) and its salts and esters, bromacil (N.3.45), lenacil (N.3.46), terbacil (N.3.47), bentazon (N.3.48), bentazon-sodium (N.3.49), pyridate (N.3.50), pyri- dafol (N.3.51), pentanochlor (N.3.52), propanil (N.3.53); diquat (N.3.54), diquat-dibromide (N.3.55), paraquat (N.3.56), paraquat-dichloride (N.3.57), paraquat-dimetilsulfate (N.3.58); N.4 protoporphyrinogen IX oxidase inhibitors: acifluorfen (N.4.1), acifluorfen sodium (N.4.2), azafenidin (N.4.3), bencarbazone (N.4.4), benzfendizone (N.4.5), bifenox (N.4.6), butafenacil (N.4.7), carfentrazone (N.4.8), carfentrazone-ethyl (N.4.9), chlormethoxyfen (N.4.10), cinidon- ethyl (N.4.11), fluazolate (N.4.12), flufenpyr (N.4.13), flufenpyr-ethyl (N.4.14), flumiclorac (N.4.15), flumiclorac-pentyl (N.4.16), flumioxazin (N.4.17), fluoroglycofen (N.4.18), fluorogly- cofen-ethyl (N.4.19), fluthiacet (N.4.20), fluthiacet-methyl (N.4.21), fomesafen (N.4.22), halosafen (N.4.23), lactofen (N.4.24), oxadiargyl (N.4.25), oxadiazon (N.4.26), oxyfluorfen (N.4.27), pentox- azone (N.4.28), profluazol (N.4.29), pyraclonil (N.4.30), pyraflufen (N.4.31), pyraflufen-ethyl (N.4.32), saflufenacil (N.4.33), sulfentrazone (N.4.34), thidiazimin (N.4.35), tiafenacil (N.4.36), tri- fludimoxazin (N.4.37), ethyl [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4- tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetate ((N.4.38) CAS 353292-31-6), N-ethyl-3- (2,6-dichloro-4-trifluoro-methylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide ((N.4.39) CAS 452098-92-9), N tetrahydrofurfuryl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1H-pyra- zole-1-carboxamide ((N.4.40) CAS 915396-43-9), N-ethyl-3-(2-chloro-6-fluoro-4-trifluorome- thyl¬phenoxy)-5-methyl-1H-pyrazole-1-carboxamide ((N.4.41) CAS 452099-05-7), N tetrahy- dro¬furfuryl-3-(2-chloro-6-fluoro-4-trifluoro¬methylphenoxy)-5-methyl-1H-pyrazole-1-carbox- amide ((N.4.42) CAS 452100-03-7), 3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H- benzo[1,4]oxazin-6-yl]-1,5-dimethyl-6-thioxo-[1,3,5]triazinan-2,4-dione ((N.4.43) CAS 451484- 50-7), 2-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-4,5,6,7-tetra- hydro-isoindole-1,3-dione ((N.4.44) CAS 1300118-96-0), 1-methyl-6-trifluoro¬methyl-3-(2,2,7-tri- fluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-1H-pyrimidine-2,4-dione ((N.4.45) CAS 1304113-05-0), methyl (E)-4-[2-chloro-5-[4-chloro-5-(difluoromethoxy)-1H-methyl- pyrazol-3-yl]-4-fluoro-phenoxy]-3-methoxy-but-2-enoate ((N.4.46) CAS 948893-00-3), 3-[7- chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)-1H-pyrimi- dine-2,4-dione ((N.4.47) CAS 212754-02-4);
N.5 Bleacher herbicides: beflubutamid (N.5.1), diflufenican (N.5.2), fluridone (N.5.3), flurochlo- ridone (N.5.4), flurtamone (N.5.5), norflurazon (N.5.6), picolinafen (N.5.7), 4-(3-trifluorome- thyl¬phenoxy)-2-(4-trifluoromethylphenyl)¬pyrimidine ((N.5.8) CAS 180608-33-7); benzobicyclon (N.5.9), benzofenap (N.5.10), bicyclopyrone (N.5.11), clomazone (N.5.12), fenquintrione (N.5.13), isoxaflutole (N.5.14), mesotrione (N.5.15), pyrasulfotole (N.5.16), pyrazolynate (N.5.17), pyrazoxyfen (N.5.18), sulcotrione (N.5.19), tefuryltrione (N.5.20), tembotrione (N.5.21), tolpyra- late (N.5.22), topramezone (N.5.23); aclonifen (N.5.24), amitrole (N.5.25), flumeturon (N.5.26); N.6 EPSP synthase inhibitors: glyphosate (N.6.1), glyphosate-isopropylammonium (N.6.2), gly- posate-potassium (N.6.3), glyphosate-trimesium (sulfosate) (N.6.4);
N.7 Glutamine synthase inhibitors: bilanaphos (bialaphos) (N.7.1), bilanaphos-sodium (N.7.2), glufosinate (N.7.3), glufosinate-P (N.7.4), glufosinate-ammonium (N.7.5);
N.8 DHP synthase inhibitors: asulam (N.8.1);
N.9 Mitosis inhibitors: benfluralin (N.9.1), butralin (N.9.2), dinitramine (N.9.3), ethalfluralin (N.9.4), fluchloralin (N.9.5), oryzalin (N.9.6), pendimethalin (N.9.7), prodiamine (N.9.8), trifluralin (N.9.9); amiprophos (N.9.10), amiprophos-methyl (N.9.11), butamiphos (N.9.12); chlorthal (N.9.13), chlor- thal-dimethyl (N.9.14), dithiopyr (N.9.15), thiazopyr (N.9.16), propyzamide (N.9.17), tebutam (N.9.18); carbetamide (N.9.19), chlorpropham (N.9.20), flamprop (N.9.21), flamprop-isopropyl (N.9.22), flamprop-methyl (N.9.23), flamprop-M-isopropyl (N.9.24), flamprop-M-methyl (N.9.25), propham (N.9.26); N.10 VLCFA inhibitors: acetochlor (N.10.1), alachlor (N.10.2), butachlor (N.10.3), dimethachlor (N.10.4), dimethenamid (N.10.5), dimethenamid-P (N.10.6), metazachlor (N.10.7), metolachlor (N.10.8), metolachlor-S (N.10.9), pethoxamid (N.10.10), pretilachlor (N.10.11), propachlor (N.10.12), propisochlor (N.10.13), thenylchlor (N.10.14), flufenacet (N.10.15), mefenacet (N.10.16), diphenamid (N.10.17), naproanilide (N.10.18), napropamide (N.10.19), napropamide- M (N.10.20), fentrazamide (N.10.21), anilofos (N.10.22), cafenstrole (N.10.23), fenoxasulfone (N.10.24), ipfencarbazone (N.10.25), piperophos (N.10.26), pyroxasulfone (N.10.27), isoxazoline compounds of the formulae II.1, II.2, II.3, II.4, II.5, II.6, II.7, II.8 and II.9
Figure imgf000137_0001
. .
;
N.11 Cellulose biosynthesis inhibitors: chlorthiamid (N.11.1), dichlobenil (N.11.2), flupoxam (N.11.3), indaziflam (N.11.4), isoxaben (N.11.5), triaziflam (N.11.6), 1-cyclohexyl-5-pentafluor- phenyloxy-14-[1,2,4,6]thiatriazin-3-ylamine ((N.11.7) CAS 175899-01-1);
N.12 Decoupler herbicides: dinoseb (N.12.1), dinoterb (N.12.2), DNOC (N.12.3) and its salts; N.13 Auxinic herbicides: 2,4-D (N.13.1) and its salts and esters, clacyfos (N.13.2), 2,4-DB (N.13.3) and its salts and esters, aminocyclopyrachlor (N.13.4) and its salts and esters, amino- pyralid (N.13.5) and its salts such as aminopyralid-dimethylammonium (N.13.6), aminopyralid- tris(2-hydroxypropyl)ammonium (N.13.7) and its esters, benazolin (N.13.8), benazolin-ethyl (N.13.9), chloramben (N.13.10) and its salts and esters, clomeprop (N.13.11), clopyralid (N.13.12) and its salts and esters, dicamba (N.13.13) and its salts and esters, dichlorprop (N.13.14) and its salts and esters, dichlorprop-P (N.13.15) and its salts and esters, fluroxypyr (N.13.16), fluroxypyr- butometyl (N.13.17), fluroxypyr meptyl (N.13.18), halauxifen (N.13.) and its salts and esters (CAS 943832-60-8); MCPA (N.13.) and its salts and esters, MCPA-thioethyl (N.13.19), MCPB (N.13.20) and its salts and esters, mecoprop (N.13.21) and its salts and esters, mecoprop-P (N.13.22) and its salts and esters, picloram (N.13.23) and its salts and esters, quinclorac (N.13.24), quinmerac (N.13.25), TBA (2,3,6) (N.13.26) and its salts and esters, triclopyr (N.13.27) and its salts and esters, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoropyridine-2-carboxylic acid (N.13.28), benzyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoropyridine- 2-carboxylate ((N.13.29) CAS 1390661-72-9);
N.14 Auxin transport inhibitors: diflufenzopyr (N.14.1), diflufenzopyr-sodium (N.14.2), naptalam (N.14.3) and naptalam-sodium (N.14.4);
N.15 Other herbicides: bromobutide (N.15.1), chlorflurenol (N.15.2), chlorflurenol-methyl (N.15.3), cinmethylin (N.15.4), cumyluron (N.15.5), cyclopyrimorate ((N.15.6) CAS 499223-49-3) and its salts and esters, dalapon (N.15.7), dazomet (N.15.8), difenzoquat (N.15.9), difenzoquat- metilsulfate (N.15.10), dimethipin (N.15.11), DSMA (N.15.12), dymron (N.15.13), endothal (N.15.14) and its salts, etobenzanid (N.15.15), flurenol (N.15.16), flurenol-butyl (N.15.17), flur- primidol (N.15.18), fosamine (N.15.19), fosamine-ammonium (N.15.20), indanofan (N.15.21), ma- leic hydrazide (N.15.22), mefluidide (N.15.23), metam (N.15.24), methiozolin ((N.15.25) CAS 403640-27-7), methyl azide (N.15.26), methyl bromide (N.15.27), methyl-dymron (N.15.28), me- thyl iodide (N.15.29), MSMA (N.15.30), oleic acid (N.15.31), oxaziclomefone (N.15.32), pelar- gonic acid (N.15.33), pyributicarb (N.15.34), quinoclamine (N.15.35), tridiphane (N.15.36);
O) Insecticides from classes O.1 to O.29
O.1 Acetylcholine esterase (AChE) inhibitors: aldicarb (O.1.1), alanycarb (O.1.2), bendiocarb (O.1.3), benfuracarb (O.1.4), butocarboxim (O.1.5), butoxycarboxim (O.1.6), carbaryl (O.1.7), car- bofuran (O.1.8), carbosulfan (O.1.9), ethiofencarb (O.1.10), fenobucarb (O.1.11), formetanate (O.1.12), furathiocarb (O.1.13), isoprocarb (O.1.14), methiocarb (O.1.15), methomyl (O.1.16), metolcarb (O.1.17), oxamyl (O.1.18), pirimicarb (O.1.19), propoxur (O.1.20), thiodicarb (O.1.21), thiofanox (O.1.22), trimethacarb (O.1.23), XMC (O.1.24), xylylcarb (O.1.25) and triazamate (O.1.26); acephate (O.1.27), azamethiphos (O.1.28), azinphos-ethyl (O.1.29), azinphosmethyl (O.1.30), cadusafos (O.1.31), chlorethoxyfos (O.1.32), chlorfenvinphos (O.1.33), chlormephos (O.1.34), chlorpyrifos (O.1.35), chlorpyrifos-methyl (O.1.36), coumaphos (O.1.37), cyanophos (O.1.38), demeton-S-methyl (O.1.39), diazinon (O.1.40), dichlorvos/ DDVP (O.1.41), dicrotophos (O.1.42), dimethoate (O.1.43), dimethylvinphos (O.1.44), disulfoton (O.1.45), EPN (O.1.46), ethion (O.1.47), ethoprophos (O.1.48), famphur (O.1.49), fenamiphos (O.1.50), fenitrothion (O.1.51), fenthion (O.1.52), fosthiazate (O.1.53), heptenophos (O.1.54), imicyafos (O.1.55), isofenphos (O.1.56), isopropyl O-(methoxyaminothio-phosphoryl) salicylate (O.1.57), isoxathion (O.1.58), malathion (O.1.59), mecarbam (O.1.60), methamidophos (O.1.61), methidathion (O.1.62), mevinphos (O.1.63), monocrotophos (O.1.64), naled (O.1.65), omethoate (O.1.66), ox- ydemeton-methyl (O.1.67), parathion (O.1.68), parathion-methyl (O.1.69), phenthoate (O.1.70), phorate (O.1.71), phosalone (O.1.72), phosmet (O.1.73), phosphamidon (O.1.74), phoxim (O.1.75), pirimiphos- methyl (O.1.76), profenofos (O.1.77), propetamphos (O.1.78), prothiofos (O.1.79), pyraclofos (O.1.80), pyridaphenthion (O.1.81), quinalphos (O.1.82), sulfotep (O.1.83), tebupirimfos (O.1.84), temephos (O.1.85), terbufos (O.1.86), tetrachlorvinphos (O.1.87), thi- ometon (O.1.88), triazophos (O.1.89), trichlorfon (O.1.90), vamidothion (O.1.91);
O.2 GABA-gated chloride channel antagonists: endosulfan (O.2.1), chlordane (O.2.2); ethiprole (O.2.3), fipronil (O.2.4), flufiprole (O.2.5), pyrafluprole (O.2.6), pyriprole (O.2.7);
O.3 Sodium channel modulators: acrinathrin (O.3.1), allethrin (O.3.2), d-cis-trans allethrin (O.3.3), d-trans allethrin (O.3.4), bifenthrin (O.3.5), bioallethrin (O.3.6), bioallethrin S-cylclopentenyl (O.3.7), bioresmethrin (O.3.8), cycloprothrin (O.3.9), cyfluthrin (O.3.10), beta-cyfluthrin (O.3.11), cyhalothrin (O.3.12), lambda-cyhalothrin (O.3.13), gamma-cyhalothrin (O.3.14), cypermethrin (O.3.15), alpha-cypermethrin (O.3.16), beta-cypermethrin (O.3.17), theta-cypermethrin (O.3.18), zeta-cypermethrin (O.3.19), cyphenothrin (O.3.20), deltamethrin (O.3.21), empenthrin (O.3.22), esfenvalerate (O.3.23), etofenprox (O.3.24), fenpropathrin (O.3.25), fenvalerate (O.3.26), flucy- thrinate (O.3.27), flumethrin (O.3.28), tau-fluvalinate (O.3.29), halfenprox (O.3.30), heptafluthrin (O.3.31), imiprothrin (O.3.32), meperfluthrin (O.3.33), metofluthrin (O.3.34), momfluorothrin (O.3.35), permethrin (O.3.36), phenothrin (O.3.37), prallethrin (O.3.38), profluthrin (O.3.39), py- rethrin (pyrethrum) (O.3.40), resmethrin (O.3.41), silafluofen (O.3.42), tefluthrin (O.3.43), tetra- methylfluthrin (O.3.44), tetramethrin (O.3.45), tralomethrin (O.3.46) and transfluthrin (O.3.47); DDT (O.3.48), methoxychlor (O.3.49);
O.4 Nicotinic acetylcholine receptor agonists (nAChR): acetamiprid (O.4.1), clothianidin (O.4.2), cycloxaprid (O.4.3), dinotefuran (O.4.4), imidacloprid (O.4.5), nitenpyram (O.4.6), thiacloprid (O.4.7), thiamethoxam (O.4.8); (2E)-1-[(6-chloropyridin-3-yl)methyl]-N'-nitro-2-pentylidenehydra- zinecarboximidamide (O.4.9); 1-[(6-chloropyridin-3-yl)methyl]-7-methyl-8-nitro-5-propoxy- 1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridine (O.4.10); nicotine (O.4.11);
O.5 Nicotinic acetylcholine receptor allosteric activators: spinosad (O.5.1), spinetoram (O.5.2); O.6 Chloride channel activators: abamectin (O.6.1), emamectin benzoate (O.6.2), ivermectin (O.6.3), lepimectin (O.6.4), milbemectin (O.6.5);
O.7 Juvenile hormone mimics: hydroprene (O.7.1), kinoprene (O.7.2), methoprene (O.7.3); fenoxycarb (O.7.4), pyriproxyfen (O.7.5);
O.8 miscellaneous non-specific (multi-site) inhibitors: methyl bromide (O.8.1) and other alkyl hal- ides; chloropicrin (O.8.2), sulfuryl fluoride (O.8.3), borax (O.8.4), tartar emetic (O.8.5);
O.9 Selective homopteran feeding blockers: pymetrozine (O.9.1), flonicamid (O.9.2);
O.10 Mite growth inhibitors: clofentezine (O.10.1), hexythiazox (O.10.2), diflovidazin (O.10.3); etoxazole (O.10.4);
O.11 Microbial disruptors of insect midgut membranes: the Bt crop proteins: Cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34/35Ab1;
O.12 Inhibitors of mitochondrial ATP synthase: diafenthiuron (O.12.1); azocyclotin (O.12.2), cyhexatin (O.12.3), fenbutatin oxide (O.12.4), propargite (O.12.5), tetradifon (O.12.6);
O.13 Uncouplers of oxidative phosphorylation via disruption of the proton gradient: chlorfenapyr (O.13.1), DNOC (O.13.2), sulfluramid (O.13.3);
O.14 Nicotinic acetylcholine receptor (nAChR) channel blockers: bensultap (O.14.1), cartap hy- drochloride (O.14.2), thiocyclam (O.14.3), thiosultap sodium (O.14.4);
O.15 Inhibitors of the chitin biosynthesis type 0: bistrifluron (O.15.1), chlorfluazuron (O.15.2), diflubenzuron (O.15.3), flucycloxuron (O.15.4), flufenoxuron (O.15.5), hexaflumuron (O.15.6), lufenuron (O.15.7), novaluron (O.15.8), noviflumuron (O.15.9), teflubenzuron (O.15.10), tri- flumuron (O.15.11);
O.16 Inhibitors of the chitin biosynthesis type 1: buprofezin (O.16.1);
O.17 Moulting disruptors: cyromazine (O.17.1);
O.18 Ecdyson receptor agonists: methoxyfenozide (O.18.1), tebufenozide (O.18.2), halofenozide (O.18.3), fufenozide (O.18.4), chromafenozide (O.18.5);
O.19 Octopamin receptor agonists: amitraz (O.19.1);
O.20 Mitochondrial complex III electron transport inhibitors: hydramethylnon (O.20.1), acequi- nocyl (O.20.2), fluacrypyrim (O.20.3);
O.21 Mitochondrial complex I electron transport inhibitors: fenazaquin (O.21.1), fenpyroximate (O.21.2), pyrimidifen (O.21.3), pyridaben (O.21.4), tebufenpyrad (O.21.5), tolfenpyrad (O.21.6); rotenone (O.21.7);
O.22 Voltage-dependent sodium channel blockers: indoxacarb (O.22.1), metaflumizone (O.22.2), 2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]-hy- drazinecarboxamide (O.22.3), N-(3-chloro-2-methylphenyl)-2-[(4-chlorophenyl)-[4-[methyl(me- thylsulfonyl)amino]phenyl]methylene]-hydrazinecarboxamide (O.22.4);
O.23 Inhibitors of the of acetyl CoA carboxylase: spirodiclofen (O.23.1), spiromesifen (O.23.2), spirotetramat (O.23.3);
O.24 Mitochondrial complex IV electron transport inhibitors: aluminium phosphide (O.24.1), cal- cium phosphide (O.24.2), phosphine (O.24.3), zinc phosphide (O.24.4), cyanide (O.24.5);
O.25 Mitochondrial complex II electron transport inhibitors: cyenopyrafen (O.25.1), cyflumetofen (O.25.2);
O.26 Ryanodine receptor-modulators: flubendiamide (O.26.1), chlorantraniliprole (O.26.2), cyan- traniliprole (O.26.3), cyclaniliprole (O.26.4), tetraniliprole (O.26.5); (R)-3-chloro-N1-{2-methyl-4- [1,2,2,2 –tetrafluoro-1-(trifluoromethyl)ethyl]phenyl}-N2-(1-methyl-2-methyl- sulfonylethyl)phthalamide (O.26.6), (S)-3-chloro-N1-{2-methyl-4-[1,2,2,2–tetrafluoro-1-(trifluoro- methyl)ethyl]phenyl}-N2-(1-methyl-2-methylsulfonylethyl)phthalamide (O.26.7), methyl-2-[3,5-di- bromo-2-({[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}amino)benzoyl]-1,2-dime- thylhydrazinecarboxylate (O.26.8); N-[4,6-dichloro-2-[(diethyl-lambda-4-sulfanylidene)car- bamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide (O.26.9); N-[4- chloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5- (trifluoromethyl)pyrazole-3-carboxamide (O.26.10); N-[4-chloro-2-[(di-2-propyl-lambda-4-sul- fanylidene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-car- boxamide (O.26.11); N-[4,6-dichloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]- 2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide (O.26.12); N-[4,6-dibromo-2- [(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)py- razole-3-carboxamide (O.26.13); N-[2-(5-amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]- 3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide (O.26.14); 3-chloro-1-(3-chloro-2- pyridinyl)-N-[2,4-dichloro-6-[[(1-cyano-1-methylethyl)amino]carbonyl]phenyl]-1H-pyrazole-5-car- boxamide (O.26.15); 3-bromo-N-[2,4-dichloro-6-(methylcarbamoyl)phenyl]-1-(3,5-dichloro-2-pyri- dyl)-1H-pyrazole-5-carboxamide (O.26.16); N-[4-chloro-2-[[(1,1-dimethylethyl)amino]carbonyl]-6- methylphenyl]-1-(3-chloro-2-pyridinyl)-3-(fluoromethoxy)-1H-pyrazole-5-carboxamide (O.26.17); cyhalodiamide (O.26.18);
O.27. insecticidal active compounds of unknown or uncertain mode of action: afidopyropen (O.27.1), afoxolaner (O.27.2), azadirachtin (O.27.3), amidoflumet (O.27.4), benzoximate (O.27.5), bifenazate (O.27.6), broflanilide (O.27.7), bromopropylate (O.27.8), chinomethionat (O.27.9), cryolite (O.27.10), dicloromezotiaz (O.27.11), dicofol (O.27.12), flufenerim (O.27.13), flometoquin (O.27.14), fluensulfone (O.27.15), fluhexafon (O.27.16), fluopyram (O.27.17), flupyradifurone (O.27.18), fluralaner (O.27.19), metoxadiazone (O.27.20), piperonyl butoxide (O.27.21), pyflubumide (O.27.22), pyridalyl (O.27.23), pyrifluquinazon (O.27.24), sulfoxaflor (O.27.25), tioxazafen (O.27.26), triflumezopyrim (O.27.27), 11-(4-chloro-2,6-dimethylphenyl)-12- hydroxy-1,4-dioxa-9-azadispiro[4.2.4.2]-tetradec-11-en-10-one (O.27.28), 3-(4’-fluoro-2,4-dime- thylbiphenyl-3-yl)-4-hydroxy-8-oxa-1-azaspiro[4.5]dec-3-en-2-one (O.27.28), 1-[2-fluoro-4-me- thyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)-1H-1,2,4-triazole-5-amine
(O.27.29), (E/Z)-N-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide (O.27.31); (E/Z)-N-[1-[(6-chloro-5-fluoro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetam- ide (O.27.32); (E/Z)-2,2,2-trifluoro-N-[1-[(6-fluoro-3-pyridyl)methyl]-2-pyridylidene]acetamide (O.27.33); (E/Z)-N-[1-[(6-bromo-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide (O.27.34); (E/Z)-N-[1-[1-(6-chloro-3-pyridyl)ethyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide (O.27.35); (E/Z)-N-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2-difluoro-acetamide (O.27.36); (E/Z)-2-chloro-N-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2-difluoro-acetamide (O.27.37); (E/Z)-N-[1-[(2-chloropyrimidin-5-yl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide (O.27.38); (E/Z)-N-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,3,3,3-pentafluoro-propana- mide (O.27.39); N-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-thioacetamide (O.27.40); N-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-N'-isopropyl-acetam- idine (O.27.41); fluazaindolizine (O.27.42); 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isox- azol-3-yl]-2-methyl-N-(1-oxothietan-3-yl)benzamide (O.27.43); fluxametamide (O.27.44); 5-[3- [2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1H-pyrazole (O.27.45); 3-(benzoylmethyl- amino)-N-[2-bromo-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]-6-(trifluoromethyl)phe- nyl]-2-fluoro-benzamide (O.27.46); 3-(benzoylmethylamino)-2-fluoro-N-[2-iodo-4-[1,2,2,2-tetra- fluoro-1-(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]-benzamide (O.27.47); N-[3-[[[2-iodo- 4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]amino]carbonyl]phenyl]- N-methyl-benzamide (O.27.48); N-[3-[[[2-bromo-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6- (trifluoromethyl)phenyl]amino]carbonyl]-2-fluorophenyl]-4-fluoro-N-methyl-benzamide (O.27.49); 4-fluoro-N-[2-fluoro-3-[[[2-iodo-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6-(trifluorome- thyl)phenyl]amino]carbonyl]phenyl]-N-methyl-benzamide (O.27.50); 3-fluoro-N-[2-fluoro-3-[[[2- iodo-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6(trifluoromethyl)phenyl]amino]carbonyl]phe- nyl]-N-methyl-benzamide (O.27.51); 2-chloro-N-[3-[[[2-iodo-4-[1,2,2,2-tetrafluoro-1-(trifluorome- thyl)ethyl]-6-(trifluoromethyl)phenyl]amino]carbonyl]phenyl]-3-pyridinecarboxamide (O.27.52); 4- cyano-N-[2-cyano-5-[[2,6-dibromo-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]car- bamoyl]phenyl]-2-methyl-benzamide (O.27.53); 4-cyano-3-[(4-cyano-2-methyl-benzoyl)amino]- N-[2,6-dichloro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]-2-fluoro-benzamide (O.27.54); N-[5-[[2-chloro-6-cyano-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]car- bamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide (O.27.55); N-[5-[[2-bromo-6-chloro-4- [2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano- 2-methyl-benzamide (O.27.56); N-[5-[[2-bromo-6-chloro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluorome- thyl)propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide (O.27.57); 4-cy- ano-N-[2-cyano-5-[[2,6-dichloro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]car- bamoyl]phenyl]-2-methyl-benzamide (O.27.58); 4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1,2,2,2- tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide (O.27.59); N-[5-[[2-bromo-6-chloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cy- ano-phenyl]-4-cyano-2-methyl-benzamide (O.27.60); 2-(1,3-dioxan-2-yl)-6-[2-(3-pyridinyl)-5-thia- zolyl]-pyridine; 2-[6-[2-(5-fluoro-3-pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine (O.27.61); 2 [6 [2 (3 pyridinyl) 5 thiazolyl] 2 pyridinyl] pyrimidine (O.27.62); N methylsulfonyl 6 [2 (3 pyridyl)thiazol-5-yl]pyridine-2-carboxamide (O.27.63); N-methylsulfonyl-6-[2-(3-pyridyl)thiazol-5- yl]pyridine-2-carboxamide (O.27.64); N-ethyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3-methylthio- propanamide (O.27.65); N-methyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3-methylthio-propana- mide (O.27.66); N,2-dimethyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3-methylthio-propanamide (O.27.67); N-ethyl-2-methyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3-methylthio-propanamide (O.27.68); N-[4-chloro-2-(3-pyridyl)thiazol-5-yl]-N-ethyl-2-methyl-3-methylthio-propanamide (O.2769.); N-[4-chloro-2-(3-pyridyl)thiazol-5-yl]-N,2-dimethyl-3-methylthio-propanamide (O.27.70); N-[4-chloro-2-(3-pyridyl)thiazol-5-yl]-N-methyl-3-methylthio-propanamide (O.27.71); N-[4-chloro-2-(3-pyridyl)thiazol-5-yl]-N-ethyl-3-methylthio-propanamide (O.27.72); 1-[(6-chloro-3- pyridinyl)methyl]-1,2,3,5,6,7-hexahydro-5-methoxy-7-methyl-8-nitro-imidazo[1,2-a]pyridine (O.27.73); 1-[(6-chloropyridin-3-yl)methyl]-7-methyl-8-nitro-1,2,3,5,6,7-hexahydroimidazo[1,2- a]pyridin-5-ol (O.27.74); 1-isopropyl-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide (O.27.75); 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide (O.27.76); N,5-dimethyl-N-pyridazin-4-yl-1-(2,2,2-trifluoro-1-methyl-ethyl)pyrazole-4-carbox- amide (O.27.77); 1-[1-(1-cyanocyclopropyl)ethyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4- carboxamide (O.27.78); N-ethyl-1-(2-fluoro-1-methyl-propyl)-5-methyl-N-pyridazin-4-yl-pyrazole- 4-carboxamide (O.27.79); 1-(1,2-dimethylpropyl)-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-car- boxamide (O.27.80); 1-[1-(1-cyanocyclopropyl)ethyl]-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4- carboxamide (O.27.81); N-methyl-1-(2-fluoro-1-methyl-propyl]-5-methyl-N-pyridazin-4-yl-pyra- zole-4-carboxamide (O.27.82); 1-(4,4-difluorocyclohexyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyra- zole-4-carboxamide (O.27.83); 1-(4,4-difluorocyclohexyl)-N,5-dimethyl-N-pyridazin-4-yl-pyra- zole-4-carboxamide (O.27.84), N-(1-methylethyl)-2-(3-pyridinyl)-2H-indazole-4-carboxamide (O.27.85); N-cyclopropyl-2-(3-pyridinyl)-2H-indazole-4-carboxamide (O.27.86); N-cyclohexyl- 2-(3-pyridinyl)-2H-indazole-4-carboxamide (O.27.87); 2-(3-pyridinyl)-N-(2,2,2-trifluoroethyl)-2H- indazole-4-carboxamide (O.27.88); 2-(3-pyridinyl)-N-[(tetrahydro-2-furanyl)methyl]-2H-indazole- 5-carboxamide (O.27.89); methyl 2-[[2-(3-pyridinyl)-2H-indazol-5-yl]carbonyl]hydrazinecarbox- ylate (O.27.90); N-[(2,2-difluorocyclopropyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-carboxamide (O.27.91); N-(2,2-difluoropropyl)-2-(3-pyridinyl)-2H-indazole-5-carboxamide (O.27.92); 2-(3-pyri- dinyl )-N-(2-pyrimidinylmethyl )-2H-indazole-5-carboxamide (O.27.93); N-[(5-methyl-2-pyrazi- nyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-carboxamide (O.27.94), N-[3-chloro-1-(3-pyridyl)pyra- zol-4-yl]-N-ethyl-3-(3,3,3-trifluoropropylsulfanyl)propanamide (O.27.95); N-[3-chloro-1-(3- pyridyl)pyrazol-4-yl]-N-ethyl-3-(3,3,3-trifluoropropylsulfinyl)propanamide (O.27.96); N-[3-chloro- 1-(3-pyridyl)pyrazol-4-yl]-3-[(2,2-difluorocyclopropyl)methylsulfanyl]-N-ethyl-propanamide (O.27.97); N-[3-chloro-1-(3-pyridyl)pyrazol-4-yl]-3-[(2,2-difluorocyclopropyl)methylsulfinyl]-N- ethyl-propanamide (O.27.98); sarolaner (O.27.99), lotilaner (O.27.100). The active substances referred to as component 2, their preparation and their activity e. g. against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commer- cially available. The compounds described by IUPAC nomenclature, their preparation and their pesticidal activity are also known (cf. Can. J. Plant Sci.48(6), 587-94, 1968; EP-A 141317; EP- A 152031; EP-A 226917; EP-A 243970; EP-A 256503; EP-A 428941; EP-A 532022; EP-A 1028125; EP-A 1035122; EP-A 1201648; EP-A 1122244, JP 2002316902; DE 19650197; DE 10021412; DE 102005009458; US 3,296,272; US 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501; WO 01/56358; WO 02/22583; WO 02/40431; WO 03/10149; WO 03/11853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491; WO 04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07/90624, WO 10/139271, WO 11/028657, WO 12/168188, WO 07/006670, WO 11/77514; WO 13/047749, WO 10/069882, WO 13/047441, WO 03/16303, WO 09/90181, WO 13/007767, WO 13/010862, WO 13/127704, WO 13/024009, WO 13/24010, WO 13/047441, WO 13/162072, WO 13/092224, WO 11/135833, CN 1907024, CN 1456054, CN 103387541, CN 1309897, WO 12/84812, CN 1907024, WO 09094442, WO 14/60177, WO 13/116251, WO 08/013622, WO 15/65922, WO 94/01546, EP 2865265, WO 07/129454, WO 12/165511, WO 11/081174, WO 13/47441). The present invention furthermore relates to agrochemical compositions comprising a mixture of at least one compound I (component 1) and at least one further active substance useful for plant protection, e. g. selected from the groups A) to O) (component 2), and if desired one suitable solvent or solid carrier. Furthermore, combating harmful fungi with a mixture of compounds of formula (I) and at least one fungicide from groups A) to O), as described above, is more efficient than combating those fungi with individual compounds (I) or individual fungicides from groups A) to O).
By applying compounds of formula (I) together with at least one active substance from groups A) to O) a synergistic effect can be obtained, i.e. more then simple addition of the individual effects is obtained (synergistic mixtures).
This can be obtained by applying the compounds (I) and at least one further active substance simultaneously, either jointly (e. g. as tank-mix) or seperately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active substance applied first still occurs at the site of action in a sufficient amount at the time of application of the further active substance(s). The order of application is not essential for working of the present invention. When applying compound I and a pesticide II sequentially the time between both applications may vary e. g. between 2 hours to 7 days. Also a broader range is possible ranging from 0.25 hour to 30 days, preferably from 0.5 hour to 14 days, particularly from 1 hour to 7 days or from 1.5 hours to 5 days, even more preferred from 2 hours to 1 day.
In the binary mixtures and compositions according to the invention the weight ratio of the compo- nent 1) and the component 2) generally depends from the properties of the active components used, usually it is in the range of from 1:10,000 to 10,000:1, often it is in the range of from 1:100 to 100:1, regularly in the range of from 1:50 to 50:1, preferably in the range of from 1:20 to 20:1, more preferably in the range of from 1:10 to 10:1, even more preferably in the range of from 1:4 to 4:1 and in particular in the range of from 1:2 to 2:1.
According to further embodiments of the binary mixtures and compositions, the weight ratio of the component 1) and the component 2) usually is in the range of from 1000:1 to 1:1, often in the range of from 100: 1 to 1:1, regularly in the range of from 50:1 to 1:1, preferably in the range of from 20:1 to 1:1, more preferably in the range of from 10:1 to 1:1, even more preferably in the range of from 4:1 to 1:1 and in particular in the range of from 2:1 to 1:1.
According to a further embodiments of the binary mixtures and compositions, the weight ratio of the component 1) and the component 2) usually is in the range of from 1:1 to 1:1000, often in the range of from 1:1 to 1:100, regularly in the range of from 1:1 to 1:50, preferably in the range of from 1:1 to 1:20, more preferably in the range of from 1:1 to 1:10, even more preferably in the range of from 1:1 to 1:4 and in particular in the range of from 1:1 to 1:2.
In the ternary mixtures, i.e. compositions according to the invention comprising the component 1) and component 2) and a compound III (component 3), the weight ratio of component 1) and com- ponent 2) depends from the properties of the active substances used, usually it is in the range of from 1:100 to 100:1, regularly in the range of from 1:50 to 50:1, preferably in the range of from 1:20 to 20:1, more preferably in the range of from 1:10 to 10:1 and in particular in the range of from 1:4 to 4:1, and the weight ratio of component 1) and component 3) usually it is in the range of from 1:100 to 100:1, regularly in the range of from 1:50 to 50:1, preferably in the range of from 1:20 to 20:1, more preferably in the range of from 1:10 to 10:1 and in particular in the range of from 1:4 to 4:1.
Any further active components are, if desired, added in a ratio of from 20:1 to 1:20 to the compo- nent 1).
These ratios are also suitable for inventive mixtures applied by seed treatment. Preference is also given to mixtures comprising as component 2) at least one active substance selected from: A) Respiration inhibitors
Inhibitors of complex III at Qo site (e.g. strobilurins): azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3- methoxy-acrylic acid methyl ester and 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylidene- aminooxymethyl)-phenyl)-2-methoxyimino-N-methyl-acetamide, pyribencarb,triclopyricarb/chlo- rodincarb, famoxadone, fenamidone;inhibitors of complex III at Qi site: cyazofamid, amisulbrom, [(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl) amino]-6-methyl-4, 9-di- oxo-1, 5-dioxonan-7-yl]2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4- methoxy-pyridine-2-carbonyl]amino]-6-methyl-4, 9-dioxo-1, 5-dioxonan-7-yl] 2-methylpropano- ate, [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine-2-car- bonyl)amino]-6-methyl-4, 9-dioxo-1, 5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8- benzyl-3-[[3-(1, 3-benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4, 9-dioxo-1, 5-dioxonan-7-yl] 2-methylpropanoate;
inhibitors of complex II (e. g. carboxamides): benodanil, bixafen, boscalid, carboxin, fen- furam,fluopyram, flutolanil, fluxapyroxad, furametpyr, isopyrazam, mepronil, oxycarboxin,pen- flufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, N-(4'-trifluoromethylthiobiphenyl-2-yl)- 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N-(2-(1, 3,3-trimethyl-butyl)-phenyl)-1, 3- dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, N-[9-(dichloromethylene)-1, 2, 3,4-tetrahydro-1, 4- methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide;
Other respiration inhibitors (e.g. complex I, uncouplers): diflumetorim, (5,8-difluoroquinazolin- 4-yl)-[2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl)-amine;
nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam; ferimzone; organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide;
ametoctradin; and silthiofam;
B) Sterol biosynthesis inhibitors (SBI fungicides) C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole, bitertanol,bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole,fenbuconazole, flu- quinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole,ipconazole, metconazole, my- clobutanil, oxpoconazole, paclobutrazole, penconazole,propiconazole, prothioconazole, sime- conazole, tebuconazole, tetraconazole, triadimefon,triadimenol, triticonazole, uniconazole; imid- azoles: imazalil, pefurazoate, prochloraz,triflumizol; pyrimidines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforine;
Delta14-reductase inhibitors: aldimorph, dodemorph, dodemorph-acetate,fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine;
Inhibitors of 3-keto reductase: fenhexamid;
Nucleic acid synthesis inhibitors
phenylamides or acyl amino acid fungicides: benalaxyl, benalaxyl-M, kiralaxyl,metalaxyl, met- alaxyl-M (mefenoxam), ofurace, oxadixyl;
others: hymexazole, octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, 5-fluoro-2-(p-tol- ylmethoxy) pyrimidin-4-amine, 5-fluoro-2-(4-fluorophenylmethoxy) pyrimidin-4-amine;
Inhibitors of cell division and cytoskeleton
tubulin inhibitors, such as benzimidazoles, thiophanates: benomyl, carbendazim,fuberidazole, thi- abendazole, thiophanate-methyl; triazolopyrimidines: 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2, 4, 6-trifluorophenyl)-[1, 2,4]triazolo[1, 5-a]pyrimidine
other cell division inhibitors: diethofencarb, ethaboxam, pencycuron, fluopicolide,zoxamide, met- rafenone, pyriofenone;
Inhibitors of amino acid and protein synthesis
methionine synthesis inhibitors (anilino-pyrimidines): cyprodinil, mepanipyrim,pyrimethanil;
protein synthesis inhibitors: blasticidin-S, kasugamycin, kasugamycin hydrochloridehydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
Signal transduction inhibitors
MAP / histidine kinase inhibitors: fluoroimid, iprodione, procymidone, vinclozolin,
fenpiclonil, fludioxonil;
G protein inhibitors: quinoxyfen;
Lipid and membrane synthesis inhibitors
Phospholipid biosynthesis inhibitors: edifenphos, iprobenfos, pyrazophos,
isoprothiolane;lipid peroxidation: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;phospholipid biosynthesis and cell wall deposition: dimethomorph, flumorph,mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate and N-(1-(1-(4-cy- anophenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
compounds affecting cell membrane permeability and fatty acides: propamocarb,propamocarb- hydrochlorid
Inhibitors with Multi Site Action
inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide,
copper oxychloride, basic copper sulfate, sulfur;thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, metiram, propineb,thiram, zineb, ziram;organochlorine compounds (e.g. phthalimides, sulfamides, chloronitriles): anilazine,chlorothalonil, captafol, captan, folpet, di- chlofluanid, dichlorophen, flusulfamide,hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, N (4 chloro 2 nitro phenyl) N ethyl 4 methyl benzenesulfonamide;guani dines and others: guanidine, dodine, dodine free base, guazatine, guazatineacetate,iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianon;
Cell wall synthesis inhibitors
inhibitors of glucan synthesis: validamycin, polyoxin B; melanin synthesis inhibitors:pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil;
Plant defence inducers
acibenzolar-S-methyl, probenazole, isotianil, tiadinil, prohexadione-calcium;phosphonates: fosetyl, fosetyl-aluminum, phosphorous acid and its salts;
Unknown mode of action
bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclomezine,difen- zoquat, difenzoquat-methylsulfate, diphenylamin, fenpyrazamine, flumetover,flusulfamide, flutianil, methasulfocarb, nitrapyrin, nitrothal-isopropyl, oxin-copper, proquinazid,tebufloquin, te- cloftalam, triazoxide, 2-butoxy-6-iodo-3-propylchromen-4-one, N-(cyclopropylmethoxyimino-( 6-difluoro-methoxy-2, 3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N'- (4-(4-chloro-3-trifluoromethyl-phenoxy)-2, 5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2, 5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine,
N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, 2-[1-[2-(5-methyl-3-trifluoromethyl-pyrazole-1-yl)-acetyl]-piperidin-4-yl)-thiazole- 4-carboxylic acid methyl-(1, 2, 3,4-tetrahydro-naphthalen-1-yl)-amide, 2-[1-[2-(5-methyl-3- trifluoromethyl-pyrazole-1-yl)-acetyl]-piperidin-4-yl)-thiazole-4-carboxylic acid methyl-(R)- 1,2, 3,4-tetrahydro-naphthalen-1-yl-amide,
1-[4-[4-[5-(2,6-difluorophenyl)-4, 5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]- 2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, methoxy-acetic acid
6-tert-butyl-8-fluoro-2, 3-dimethyl-quinolin-4-yl ester, N-Methyl-2-[1-[(5-methyl-3-trifluoromethyl- 1H-pyrazol-1-yl)-acetyl]-piperidin-4-yl)-N-[(1R)-1, 2, 3,4-tetrahydronaphthalen-1-yl]-4-thia- zolecarboxamide,
3-[5-(4-methylphenyl)-2, 3-dimethyl-isoxazolidin-3-yl]-pyridine, 3-[5-(4- chloro-phenyl)-2, 3-dimethyl-isoxazolidin-3-yl]-pyridine (pyrisoxazole), N-(6-methoxy-pyridin-3- yl) cyclopropanecarboxylic acid amide, 5-chloro-1-(4, 6-dimethoxy-pyrimidin-2-yl)-2-methyl- 1Hbenzoimidazole,
2-(4-chloro-phenyl)-N-[4-(3, 4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide; Accordingly, the present invention furthermore relates to mixtures comprising one compound of the formula I (component 1) and one pesticide II (component 2), wherein pesticide II is selected from the column "Co.2" of the B-1 to B-727 of Table B. A further embodiment relates to the mixtures B-1 to B-727 listed in Table B, where a row of Table B corresponds in each case to a fungicidal mixture comprising as active components one the individualized compounds of formula (I), i.e. the compounds defined in any of the first to forty nine embodiments (component 1 in column“Co.1”) and the respective pesticide II from groups A) to O) (component 2) stated in the row in question. Preferably, the compositions described in Table B comprise the active components in syn- ergistically effective amounts. Table B: Mixtures comprising as active components one indiviualized compound of the fomula I (in column Co. 1), and as component 2) (in column Co. 2) one pesticide from groups A) to O) [which is coded e. g. as (A.1.1) for azoxystrobin as defined above].
Mix . .1 .2 Mix . .1 .2 Mix . .1 .2
Figure imgf000147_0001
Figure imgf000148_0001
Figure imgf000149_0001
Figure imgf000150_0001
Figure imgf000151_0001
Figure imgf000152_0001
The mixtures of active substances can be prepared as compositions comprising besides the ac- tive ingredients at least one inert ingredient (auxiliary) by usual means, e. g. by the means given for the compositions of compounds of formula (I).
Concerning usual ingredients of such compositions reference is made to the explanations given for the compositions containing compounds of formula (I).
The mixtures of active substances according to the present invention are suitable as fungicides, as are the compounds of formula (I). They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, especially from the classes of the which de- rive especially from the following classes or are closely related to any of them: Solani, for example, but not limited to the genus Alternaria; fusarium or Rhizoctonia; Sorokiniana, for example, but not limited to the genus Bipolaris; Cinerea, for example, not limited to Botyris; Miyabeanus, not limited to Cochliobolus; Orbiculare, not limited to Colletotrichum; Teres, but not limited to Drechslera or Pyrenophora ; Repentis, but not limited to Tritici; Erysiphe spp. ; Culmorum, but not limited to Fusarium; Nivale, but not limited to Microdochium; Monilinia spp. e. g. M. laxa, M. fructicola and M. fructigena; Oryzae, but not limited to Bipolaris, Entyloma, Hemileia, Pyricularia and Rocladium; Pachyrhizi, but not limited to Phakopspora; Sclerotiorium, but not limited to Sclerotinia; Tritici, but not limited to Zymoseptoria; Basicola, but not limited to Thielaviopsis; Maydis, but not limited to Ustilago.
The mixtures of the active substances further show phytopathogenic activity against pathogens that are resistant to complex 2 or complex 3 respiratory chain inhibitors e.g: in Sclerotinia sclero- tiorum and/or Botyris cinerea. Preparative examples:
With appropriate modification of the starting materials or intermediates, the procedures as de- scribed in the examples below were used to obtain further compounds of formula I. The com- pounds obtained in this manner are listed in the Table P that follows, together with physical data.
Compounds can be characterized e.g. by Liquid Chromatography Mass spectroscopy (LCMS), by 1H-NMR and/or by their melting points.
L M M h L M m h ri i n D vi ri i n
Figure imgf000153_0001
Figure imgf000154_0001
e ng pon was recor e usng a n a o e: - or rma c 1H-NMR: The signals are characterized by chemical shift (ppm, [delta]) vs. tetramethylsilane respectively, CDCl3 or DMSO as solvents, by their multiplicity and by their integral (relative number of hydrogen atoms given). The following abbreviations are used to characterize the multiplicity of the signals: m = multiplet, q = quartet, t = triplet, d = doublet and s = singlet. 1) Preparation of 5-fluoro-3-[2-(trifluoromethyl)-3-thienyl]-1H-pyrrolo[2,3-b]pyridine (EX.24): Step 1:
Figure imgf000155_0001
Dissolved compound 1 (10 g) in methanol : water (240:12 ml) mixture in a Round Bottom (RB) flask. To this flask was added NaOH (2.94 g). Allowed it to stir at room temperature (RT) for 15 minutes until it gets completely dissolved. Then added potassium Iodide (12.1 g) and Iodine (18.60 g) to the reaction mixture. Allowed it to stir at 25°C for 2 hrs. Reaction progress was monitored by Thin Layer Chromatography (TLC) and LCMS. Methanol was distilled-off from the reaction mixture. Washed the reaction mixture with saturated solution of sodium thiosulfate. Extracted it with ethyl acetate. Washed the ethyl acetate layer with brine solution and dried over Na2S04. Crude material was used for the next step. 35 g (yield 93%) of the crude solid com- pound 2 was obtained.
1 H NMR (300 MHz, DMSO-d6) δ 12.27 (s, 1 H), 8.25 (s, 1 H), 7.82 (s, 1 H), 7.56 (dd, J = 9.0, 2.6 Hz, 1 H).
Ste 2:
Figure imgf000155_0002
Dissolved compound 2 (35 g) in THF (180 ml). Allowed it to cool to 0°C. Added NaH (3.2 g) to the reaction mixture in portions at 0°C. Allowed it to stir at RT for 20 min. Then added p-TSCI (15.7 g) to reaction mixture at 0°C. Allowed it to stir at RT for 2 hrs. Reaction progress was monitored by TLC and LCMS. Reaction was cooled to 5°C and ice cold water was added to it, and it was then immediately extracted with ethyl acetate. Combined organic layer was washed with brine solution and dried over Na2S04. The solid was triturated with ethyl acetate/heptane to afford the product as a light brown solid. 54 g of the desired solid compound 3 (yield 96%) was obtained.
1 H NMR (300 MHz, DMSO-d6) δ 8.43 (s, 1 H), 8.25 (s, 1 H), 8.00 (d, J = 8.4 Hz, 2H), 7.74 (dd, J = 8.5, 2.6 Hz, 1 H), 7.43 (d, J = 8.2 Hz, 2H), 2.35 (s, 3H).
Figure imgf000155_0003
Dioxane : H2O (80:20 ml) was taken in a RB flask containing rectant1 (10 g). To this, compound 3 was added (4.5 g) followed by K2CO3 (9.9 g). Allowed it to degas for 15 min. Then added the Palladium (878 mg) catalyst to the reaction mixture. Allowed it to degas for another 5 min. Re- fluxed the reaction mixture at 110°C for 2 hrs. Reaction progress was monitored by TLC and LCMS. After completion of the reaction, the mixture was filtered through celite. Washed the celite with ethyl acetate. Washed the EA by brine and dried over Na2SO4. Crude compound was taken in methanol and stirred for 10 min. A solid was formed which was filtered and washed with methanol and dried to obtain 8.4 g of the desired product 22.
1H NMR (300 MHz, DMSO-d6) δ 8.49– 8.34 (m, 3H), 8.09 (s, 1H), 8.01 (d, J = 8.3 Hz, 2H), 7.79– 7.63 (m, 2H), 7.42 (d, J = 8.2 Hz, 2H), 2.34 (s, 3H).
Step 4:
Figure imgf000156_0001
Added DCM (120 ml) to a RB flask containing compound 22 (6 g). Added p-TSA (0.305 g) to it. Allowed it to stir at RT for 5 min. NIS (4.3 g) was added to RM portion wise. Allowed it to stir at RT for 12 hrs. Reaction progress was monitored by TLC and LCMS. After reaction completion, saturated solution of Na2S2O8 was added to the reaction mixture. It was then filtered through a filter paper. Extracted the reaction mixture with DCM. Combined DCM layer was washed with brine solution and dried over Na2SO4. Washed the crude compound with heptane by stirring it. 7.2 gm of desired solid was obtained.
1H NMR (300 MHz, DMSO-d6) δ 8.46 (s, 1H), 8.25 (s, 1H), 8.04 (d, J = 8.3 Hz, 2H), 7.92 (d, J = 5.4 Hz, 1H), 7.87 (dd, J = 8.9, 2.7 Hz, 1H), 7.44 (d, J = 8.2 Hz, 2H), 7.24 (d, J = 5.4 Hz, 1H), 2.34 (d, J = 3.7 Hz, 3H), 1.20 (d, J = 9.5 Hz, 1H).
Step 5:
Figure imgf000156_0002
DMF (90 ml) was added to a RB flask containing compound 23 (9 g). Added CuI (4.1 g). Al- lowed it to stir at RT for 5 min. Added the fluorinating reagent (10.4 g, 4.56 ml) to RM. Allowed it to reflux at 130°C for 12 hrs. Reaction progress was monitored by TLC and LCMS. After reac- tion completion, ethyl acetate and water was added. The mixture was filtered over celite.
Washed the EA layer with brine and dried over Na2SO4. Crude compound was purified by Yamazen by eluting with 15 % ethyl acetate: hexane solution.4.4 g of desired solid product 24 was obtained.
1H NMR (300 MHz, DMSO-d6) δ 8.49 (s, 1H), 8.15– 8.07 (m, 2H), 8.03 (d, J = 8.3 Hz, 2H), 7.89 (dd, J = 8.8, 2.6 Hz, 1H), 7.51 (d, J = 4.0 Hz, 1H), 7.46 (d, J = 8.2 Hz, 2H), 2.36 (s, 3H).
Step 3a: direct coupling of the 2 Trifluoromethyl thiophene 3 boronic acid
Figure imgf000158_0002
Dioxane : water (60:200 ml) mixture was added to a round bottom flask containing compound 3 (70 mg). Added the boronic acid (50 mg) and K2CO3 (71 mg) to the flask. Allowed it to degas for 15 min. Then added the Palladium catalyst (6 mg) to the reaction mixture. Allowed it to de- gas again for 5 min. Refluxed the reaction mixture at 110°C for 2 hrs. Reaction progress was monitored by TLC and LCMS. Once complete, the reaction mixture was filtered through celite. Washed thoroughly with ethyl acetate (EA). Extracted the crude compound with EA from aque- ous phase. Washed the ethyl acetate layer with brine solution and dried over Na2SO4. Crude material was purified by Yamazen purification system using 25% ethylacetate : heptane mixture as eluent.30 mg of the desired solid compound 4 was obtained.
Step 6:
Figure imgf000158_0001
Methanol (330 ml) was added to a RB flask containing compound 24 (11 g). Added NaOMe (20.25 g) to reaction mixture portion wise. solution start becoming transparent. Allowed it to stir at RT for 12 hrs. Reaction progress was monitored by TLC and LCMS. After reaction comple- tion, methanol was distilled off. Added water and ethyl acetate to the reaction mixture. Extracted the RM with ethyl acetate. Washed the EA layer with brine solution and dried over
Na2SO4.Crude compound was purified by Yamazen by eluting with 20% ethylacetate : hexane mixture.5.72 g of the desired solid product 25 was obtained.
1H NMR (300 MHz, DMSO-d6) δ 12.28 (s, 1H), 8.35– 8.27 (m, 1H), 8.03 (d, J = 5.1 Hz, 1H), 7.85– 7.69 (m, 2H), 7.53– 7.44 (m, 1H).
2) Preparation of 3-[2-(trifluoromethyl)-3-thienyl]-1H-pyrrolo[2,3-b]pyridine-5-carbonitrile (Ex.25): Step 1:
Figure imgf000158_0003
To a RB flask was added compound 6 (4 g), KI (4.6 g), NaOH (1.1 g) and mixture was dissolved in methanol (80 ml) water (8 ml) mixture. Stirred for 5 min and to this mixture, was added iodine granules (7.1 g) portion wise at 25 C. Reaction mixture was stirred at the same temperature for 6 hrs. Reaction was monitored by TLC. Methanol was evaporated completely and residue ob- tained was diluted with water and stirred for 10 min. Off-white suspension was formed. Filtered it through Buchner funnel. Solid obtained was washed with water. Solid was dried under vac- uum at 48°C for 1 h.6.5 g of the off-white solid 7 was obtained. LCMS showed ~19% SM 1. Alternatively, the reaction can also be carried out in DMF. To a RB flask was added compound 6, KOH (3.0 eq) and the mixture was dissolved in DMF (10 vol). Stirred for 5 min and to this was added iodine granules (1.2 eq) portion wise at 25°C. Reaction mixture was stirred at same tem- perature for 4 hrs. Reaction was monitored by TLC. After completion of the reaction, ice water (100 ml) was added. A solid was precipitated. Stirred it for 15 min. Filtered it through Buchner funnel and washed with water and heptane. Solid was dried under vacuum at 50°C afforded 6.4 g of white solid compound.
1H NMR (300 MHz, DMSO-d6) δ 8.63 (d, J = 1.8 Hz, 1H), 8.24 (d, J = 1.8 Hz, 1H), 7.96 (s, 1H). Step 2:
Figure imgf000159_0001
300 ml) was added NaH (2.7 g) portion wise at 0°C. Resulting mixture was stirred at the same temperature for 30 min. TsCl (12.8 g) was added portion wise at 0°C. Reaction mixture was warmed to 25°C and stirred for 2 h.7 was consumed completely as indicated by TLC. Reaction was cooled to 5°C and to this mixture was added ice cold water (30 ml), and it was then immediately extracted with ethyl acetate (long time work up leads to de-tosylation side product). Combined organic layer was washed with brine and dried over Na2SO4. Evaporated the organic layer up to volume 75%. To this was n- Heptane added until the solid was precipitated. It was filtered and dried to afford 18 g of the de- sired compound 8.
1H NMR (300 MHz, DMSO-d6) δ 8.83 (d, J = 1.8 Hz, 1H), 8.45– 8.33 (m, 2H), 8.04 (d, J = 8.4 Hz, 2H), 7.46 (d, J = 8.1 Hz, 2H), 2.36 (s, 3H).
Step 3:
Figure imgf000159_0002
(18.5 g) were taken in a mixture of dioxane (320ml) and water (68ml) in a RB flask. Resulting mixture was degassed for 10 min. To this was added PdCl2(dppf) (1.64 g) and again degassed for 5 min. Resulting reaction was stirred and heated at 110 C for 2 hrs under nitrogen atmosphere. Reaction was monitored by TLC. After completion of reaction cooled it to RT. Filtered the reaction through celite bed and washed with DCM. Filtrate was washed with water and brine. Organic layer was dried over Na2SO4 and evaporated completely. Crude compound was taken in methanol and stirred for 10 min. Filtered it and the solid was washed with methanol. It was dried under vacuum to afford 14 g of the desired product 9 as brown solid.
1H NMR (300 MHz, DMSO-d6) δ 9.03 (d, J = 1.8 Hz, 1H), 8.86 (d, J = 1.8 Hz, 1H), 8.53 (s, 1H), 8.18 (dd, J = 2.6, 1.2 Hz, 1H), 8.05 (d, J = 8.4 Hz, 2H), 7.82– 7.61 (m, 2H), 7.45 (d, J = 8.2 Hz, 2H), 2.35 (s, 3H).
Step 4:
Figure imgf000160_0001
To a stirred solution of compound 9 (4.5 g) in dry DCM (100 ml) was added p-TSA (561 mg). Cooled the reaction mixture to 0 °C and to this was added N-Iodo succinimide (2.79 g) portion wise. Allowed the reaction mixture to come at 25°C and stirred for 12 h. Reaction was moni- tored by LCMS. After completion, added Na2S2O3 solution and DCM. Stirred and separated the organic layer and washed with water and brine. Organic layer was dried over Na2SO4. Evapo- rated the solvent completely. Semisolid mass was dissolved in 4 x DCM and added n-Heptane (~50 x). Stirred and the precipitated solid was filtered off and dried.4.2 g of the expected prod- uct 10 was obtained as a brown solid.
1H NMR (300 MHz, DMSO-d6) δ 8.87 (d, J = 1.7 Hz, 1H), 8.56 (d, J = 1.8 Hz, 1H), 8.37 (s, 1H), 8.08 (d, J = 8.3 Hz, 2H), 7.94 (d, J = 5.4 Hz, 1H), 7.47 (d, J = 8.2 Hz, 2H), 7.30 (d, J = 5.4 Hz, 1H), 2.37 (s, 3H).
Step 5:
Figure imgf000160_0002
To a RB flask was added compound 10 (12 g), fluorinating agent (13.6 g), CuI (3.6 g) and DMF (80 ml) under nitrogen atmosphere. Resulting reaction mixture was heated and stirred at 130°C for 12 hrs. Reaction was monitored by TLC and LCMS. After completion of the reaction, the flask was cooled to RT and added ice water to it followed by ethyl acetate addition. A solid was precipitated. Filtered it through a celite bed and washed with ethyl acetate. Organic layer was separated and aqueous phase was extracted two times with ethyl acetate. Combined organic layer was washed with water (2 x 50 ml) and brine (15 ml). Organic layer was dried over Na2SO4 and evaporated completely. Crude compound was purified by flash column chromatog- raphy. Pure compound was eluted with 15-20% ethyl acetate in Heptane. Evaporation of solvent afforded 9 g of white solid compound.
1H NMR (300 MHz, DMSO-d6) δ 8.90 (d, J = 1.8 Hz, 1H), 8.57 (d, J = 1.9 Hz, 1H), 8.19 (s, 1H), 8.12 (d, J = 5.1 Hz, 1H), 8.07 (d, J = 8.4 Hz, 2H), 7.56 (dd, J = 5.1, 1.4 Hz, 1H), 7.48 (d, J = 8.2 Hz, 2H), 2.36 (s, 3H).
Step 6:
Figure imgf000161_0001
To a stirred solution of compound 11 (9 g) in MeOH (270 ml) was added NaOMe(16.2 g) portion wise at 25°C and the resulting reaction mixture was stirred at 25°C for 12 hrs. The reaction was monitored by TLC and LCMS. After completion of the reaction by TLC and LCMS, the solvent was evaporated. The residue obtained was taken in water and was extracted with ethyl acetate (3 x 100 ml). The combined organic layer was washed with brine and dried over Na2SO4 and the solvent was evaporated. The crude product was purified by flash column chromatography using Yamazen purification system and the product was eluted in 20-25% ethyl acetate/Heptane. Evaporation of solvent afforded 4.3 g of white solid compound 12.
1H NMR (300 MHz, DMSO-d6) δ 12.77 (s, 1H), 8.71 (d, J = 1.9 Hz, 1H), 8.48 (d, J = 1.7 Hz, 1H), 8.07 (d, J = 5.1 Hz, 1H), 7.85 (d, J = 2.3 Hz, 1H), 7.55– 7.49 (m, 1H). 3) 1-acetyl-3-[2-(trifluoromethyl)-3-thienyl]indole-5-carbonitrile(Ex.11):
Step 1:
C
Figure imgf000161_0002
ompound 13 (15 g) was taken in methanol (300 ml) and water (30 ml) mixture and NaOH (4.6 g) and KI (20.89 g) were added. Iodine (30.51 g) was added portion wise at RT. Reaction mix- ture was stirred at RT for 6 hr. Reaction was monitored using LCMS & TLC. Reaction mixture was diluted with water (1000 ml) and the precipitated solid was filtered-off and dried under vac- uum. Yellow solid obtained was dissolved in DCM and dried over sodium sulphate and concen- trated under vacuum.25 g of pure solid compound 14 was obtained.
1H NMR (300 MHz, DMSO-d6) δ 12.09 (s, 1H), 7.82– 7.73 (m, 2H), 7.64– 7.47 (m, 2H).
Figure imgf000163_0001
Compound 14 (22 g) was taken in dry THF (200 ml) and cooled to 0°C and added NaH portion wise under stirring. After 30 minutes, tosyl chloride was added portion wise and the reaction mixture was stirred at RT for 3 hr and reaction was monitored by TLC. Reaction was quenched with saturated ammonium chloride solution and diluted with ethyl acetate. Aqueous layer was extracted with ethyl acetate and the combined organic layer was again washed with water and brine. Organic layer was dried over sodium sulphate and concentrated under vacuum. Ethyl ac- etate was evaporated to minimum quantity and was diluted with heptane and stirred for 1hr. A solid was obtained which was filtered and dried under vacuum.33 g of the pure solid compound 15 was obtained.
1H NMR (300 MHz, DMSO-d6) δ 8.31 (s, 1H), 8.13 (d, J = 8.6 Hz, 1H), 7.99 (d, J = 8.4 Hz, 2H), 7.91– 7.78 (m, 2H), 7.44 (d, J = 8.2 Hz, 2H), 2.34 (s, 3H).
Step 3:
Figure imgf000163_0002
Compound 15 (10 g), Thiophene boronic acid and K2CO3 were taken in Dioxane (120 ml): Wa- ter(15ml) mixture in a two neck RB flask equipped with Nitrogen balloon and reflux condenser. Reaction mass was degassed for 20 min. Palladium catalyst was added and reaction mass was again degassed for 3 min. Reaction mixture was refluxed at 110°C for 2 hrs under Nitrogen. Re- action progress was monitor by TLC. After completion of the reaction, the mixture was filtered through a bed of celite. Filtrate was diluted with ethyl acetate. Ethyl acetate layer was washed with water and brine and concentrated. Crude material was taken in 80 ml methanol and stirred for 45 min at RT. Solid obtained is filtered and wash with cold methanol to get 8.4 g white solid product.
1H NMR (300 MHz, DMSO-d6) δ 8.50 (s, 1H), 8.40 (s, 1H), 8.22– 8.08 (m, 2H), 7.98 (d, J = 8.3 Hz, 2H), 7.82 (d, J = 8.7 Hz, 1H), 7.70 (d, J = 1.8 Hz, 2H), 7.41 (d, J = 8.2 Hz, 2H), 2.31 (s, 3H). Step 4:
Figure imgf000164_0001
Compound 16 (3.7 g) was taken in DCM (60 ml) and Methanol (10 ml) under nitrogen atmos- phere and cooled with ice. To this, a stirred solution of PTSA.H2O was added. In another round bottom flask, NIS (0.95 eq) was taken and dissolve in 20 ml DCM and 3 ml Methanol. This was added dropwise to the reaction flask with stirring. Reaction mixture was stirred at 0°C for 45 min and reaction monitoring was done by HPLC. Depending upon the remaining starting material amount added an extra amount (0.05 eq) NIS. Reaction was quenched with water and diluted with DCM. DCM layer was separated and taken in a separating funnel and it was washed with water and brine solution. DCM layer was dried and concentrated under vacuum. Crude material was taken in methanol (6 ml) and stirred at RT for 15 min. The solid thus obtained was filtered and dried under vacuum.4.0 g of the desired product 17 was obtained.
1H NMR (300 MHz, DMSO-d6) δ 8.26 (s, 1H), 8.19 (d, J = 8.5 Hz, 1H), 8.03 (d, J = 8.3 Hz, 2H), 7.97 (s, 1H), 7.94 (d, J = 5.4 Hz, 1H), 7.82 (d, J = 8.3 Hz, 1H), 7.44 (d, J = 8.2 Hz, 2H), 7.25 (d, J = 5.4 Hz, 1H), 2.34 (s, 3H).
Step 5:
Figure imgf000164_0002
Compound 17 (6 g) and CuI were taken in DMF (55 ml) and stirred under nitrogen atmosphere. To this solution at RT was added the fluorinating reagent dropwise under stirring. Reaction mix- ture was heated overnight under nitrogen. Reaction completion was monitor by TLC and HPLC. Reaction was quenched with water (100 ml) and diluted with ethyl acetate (150 ml). This was filtered through celite. The aqueous layer was separated and the combined organic layer was washed again with water and brine. Organic layer was then dried over sodium sulphate and concentrated. Purification with 15-20% ethylacetate:heptane solvent system afforded 4.53g (85%) of the desired product 18.
1H NMR (300 MHz, DMSO-d6) δ 8.20 (d, J = 8.7 Hz, 1H), 8.11 (d, J = 4.9 Hz, 2H), 8.05– 7.95 (m, 3H), 7.84 (dd, J = 8.7, 1.4 Hz, 1H), 7.51 (dd, J = 5.1, 1.4 Hz, 1H), 7.44 (d, J = 8.2 Hz, 2H), 2.34 (s, 3H). Step 3a: Direct coupling:
Figure imgf000165_0001
Compound 15 (0.682 g), [2-(trifluoromethyl)-3-thienyl] boronic acid (0.38 g) and 2N solution of Na2CO3 (0.514 g, 2.4ml) were taken in n-Butanol (5ml) in a RB flask. Resulting mixture was de- gassed for 10 min. To this, was added PdCl2(PPh3)2 (0.057 g) and again degassed for 5 min. Resulting reaction mixture was stirred and heated at 110°C for 2 hrs under nitrogen atmos- phere. Reaction completion was monitored by TLC. After completion of reaction it was cooled to RT. Filtered the reaction through celite bed and washed with ethyl acetate. Filtrate was washed with water and brine. Organic layer was dried over Na2SO4 and evaporated completely. Crude compound was purified by flash column chromatography. Pure compound was eluted with 10- 25% ethyl acetate in heptane. Evaporated solvent under vacuum. It was concentrated under vacuum to afford 0.25 g (34.70%) of the desired product 18.
1H NMR (300 MHz, DMSO-d6) δ 8.20 (d, J = 8.7 Hz, 1H), 8.11 (d, J = 4.9 Hz, 2H), 8.05– 7.95 (m, 3H), 7.84 (dd, J = 8.7, 1.4 Hz, 1H), 7.51 (dd, J = 5.1, 1.4 Hz, 1H), 7.44 (d, J = 8.2 Hz, 2H), 2.34 (s, 3H).
Step 6:
Figure imgf000165_0002
Compound (4.53) 18 was taken in methanol under nitrogen and added sodium methoxide por- tion wise under nitrogen. Reaction mixture stirred at RT overnight. The solvent was distilled off under vacuum and diluted with ethyl acetate followed by water addition. The aqueous layer was separated and the combined organic layer was washed with water and brine. Organic layer was dried and concentrated under vacuum. Crude compound was purified by column chromatog- raphy using 20-25% ethyl acetate: Heptane solvent system to obtain 2.4 g of the desired prod- uct 19.
1H NMR (300 MHz, DMSO-d6) δ 12.06 (s, 1H), 8.04 (d, J = 5.1 Hz, 1H), 7.99 (s, 1H), 7.72 (s, 1H), 7.66 (d, J = 8.5 Hz, 1H), 7.59– 7.47 (m, 2H). Step 7:
Figure imgf000166_0001
To a stirred mixture of compound 19 (0.180 g) in DCM (10 ml) was added TEA (0.186 g) and catalytic amount of DMAP (0.015g). Then added methyl chloroformate (0.07g) dropwise. Result- ing reaction mixture was stirred at 25°C for 6 h. Reaction monitoring was performed by TLC and LCMS. After reaction completion, added water and it was extracted with DCM (3 x 15 ml). Com- bined organic layer was washed with brine and dried over Na2SO4 and the solvent was evapo- rated completely. Crude product obtained was purified by flash column chromatography. Pure compound was eluted at 40% ethyl acetate in heptane. Evaporation of solvent afforded 0.18 g of white solid compound 20.
1H NMR (300 MHz, DMSO-d6) δ 8.34 (d, J = 8.7 Hz, 1H), 8.12 (d, J = 5.1 Hz, 1H), 7.99 (d, J = 11.3 Hz, 2H), 7.86 (d, J = 8.6 Hz, 1H), 7.53 (d, J = 5.1 Hz, 1H), 4.06 (s, 3H).
Step 8: Acetic anhydride
Figure imgf000166_0002
To a mixture of compound 19 (60 mg) in acetic anhydride (0.7 ml) was added TEA (0.052 g) and catalytic amount of DMAP (0.005 g). Resulting reaction mixture was stirred at 25°C for 1 h. Reaction was monitored by TLC. After completion of reaction, it was quenched with ice cold wa- ter (25 ml) and extracted with ethyl acetate (2 x 25 ml). Combined organic layer was washed with brine (25 ml). Organic layer was dried over Na2SO4 and evaporated completely. Crude compound was purified by flash column chromatography. Pure compound was eluted with 10- 15% ethyl acetate : heptane solution. Evaporation of solvent afforded 0.035 g of the solid white compound 21.
1H NMR (300 MHz, DMSO-d6) δ 8.55 (d, J = 8.6 Hz, 1H), 8.21– 8.09 (m, 2H), 7.95 (s, 1H), 7.84 (d, J = 8.6 Hz, 1H), 7.52– 7.44 (m, 1H), 2.73 (s, 3H). 4) Preparation of Methyl 6-[2-(trifluoromethyl)-3-thienyl]-4H-pyrrolo[2,3-d]thiazole-2-carboxylate (Ex.77): Step 1:
Figure imgf000166_0003
To a stirred solution of compound 1a (159 g, 1.2 mol) and triethylamine (167 mL, 1.2 mol) in t BuOH (1 L) was added DPPA (343 g, 1.2 mol) drop wise at 10oC and the mixture was heated to reflux for 16 hrs. The mixture was concentrated and purified by column (PE: EtOAc = 20:1~5:1) to give compound 2a (170 g, 69.1%) as a white solid.
1H NMR CDCl3, 400 MHz ^ 8.60 (s, 1 H), 8.56 (bs, 1 H), 7.31 (bs, 1 H) 1.56 (s, 9 H).
Step 2:
Figure imgf000167_0001
To a stirred solution of compound 2a (90 g, 1.35 mol) in DCE (1200 mL) was added NIS (135 g, 1.74 mol) portion wise at 20oC and stirred for 5 hrs. The mixture was washed with brine (200 mL), aq. Na2SO3 (200 mL), dried over Na2SO4, filtered, concentrated and purified by column (PE:EtOAc = 20:1~5:1) to give compound 3a (110 g, 75.0%) as a white solid.
1H NMR CDCl3, 400 MHz ^ 8.79 (s, 1 H), 6.53 (bs, 1 H), 1.54 (s, 9 H).
Step 3:
Figure imgf000167_0002
To a mixture of compound 3a (120 g, 0.37 mol), compound 4a (109 g, 0.55 mol) and K2CO3 (102 g, 0.74 mol) in 500 mL dioxane, 200 mL CH3CN and 200 mL water was added Pd(dppf)Cl2 (6 g, 0.037mol) and heated to 90oC for 5 hrs. Additional 2 g of Pd(dppf)Cl2 was added and the mixture was stirred for another 8 hrs. The reaction was monitored by LCMS. The mixture was concentrated and purified by column (PE:EtOAc = 2:1) to give a cis and trans isomeric mixture of compound 5a (50 g, 50%) as a yellow oil.
1H NMR CDCl3, 400 MHz ^ 8.50 (s, 1 H), 8.35 (s, 1 H), 6.84 (d, J=8.4 Hz, 1 H), 6.66 (bs, 1H), 6.54 (bs, 1H), 6.31 (d, J=4 Hz, 1 H), 5.86 (d, J=8.4 Hz, 1 H), 5.60 (d, J=4 Hz, 1 H), 4.03 (q, 2 H), 3.89 (q, 2 H), 1.39 (t, 3 H), 1.35 (t, 3H), 1.24 (s, 9 H). Step 4:
Figure imgf000167_0003
The mixture of compound 5a (50 g, 0.185 mol) in 500 mL aq.2N HCl was stirred at 90oC for 1 hr. The mixture turned black and some solid appeared. TLC (PE : EtOAc = 3:1) showed the re- action completed. The mixture was extracted with EtOAc (1 L x 3), dried over Na2SO4, filtered, concentrated and purified by column (PE: EtOAc = 10:1~3:1) to give compound 6a (11 g, 48.0%) as a white solid.
1H NMR CDCl3, 400 MHz ^ 9.62 (bs, 1H), 8.54 (s, 1 H), 7.08 (d, J=4.0 Hz, 1 H), 6.46 (d, J=4
Figure imgf000168_0001
To a solution of compound 6a (11 g, 0.0887 mol) in 200 ml THF was added NaH (4.26 g, 0.106 mol) portion wise at 0oC under N2 and stirred for 1 hr. Then TIPSCl (20.4 g, 0.106 mol) was added drop wise and stirred at 0oC~20oC for 16 h. TLC (PE: EtOAc =5:1) showed the reaction completed. The mixture was quenched with 1 ml water, extracted with EtOAc (40 mL), washed with 20 mL brine, dried over Na2SO4, filtered, concentrated and purified by column (PE : EtOAc = 50:1) to give compound 7a (23 g, crude) as a white solid.
1H NMR CDCl3, 400 MHz ^ 8.48 (s, 1 H), 7.03 (s, 1 H), 6.51 (s, 1 H), 1.79 (hep, 3 H), 1.13 (d, J=7.6 Hz, 18 H). Step 6:
Figure imgf000168_0002
To a solution of compound 7a (23 g, 0.082 mol) in 300 ml DCE was added NIS (16.4 g, 0.073 mol) portion wise at 0oC and stirred at 0oC ~20oC for 3 hrs. The reaction was monitored by LCMS. The mixture was washed with 50 mL brine, 50 mL aq. Na2S2O3, dried over Na2SO4, fil- tered, concentrated and purified by column (PE : EtOAc = 50:1) to give compound 8a (21 g, 56.1%) as a yellow oil.
1H NMR CDCl3, 400 MHz ^ 8.52 (s, 1 H), 7.03 (s, 1 H), 1.76 (hep, 3 H), 1.13 (d, J=7.6 Hz, 18 H). Step 7:
Figure imgf000168_0003
To a mixture of compound 8a (15.3 g, 0.0376 mol), compound 9 (11.5 g, 0.0414 mol) and Cs2CO3 (24.5 g, 0.0752 mol) in 150 mL dioxane, 50 mL CH3CN and 50 mL water was added Pd(dppf)Cl2 (1.5 g, 10% w) and heated to 90oC under N2 for 16 hrs. TLC (PE: EtOAc = 3:1) showed the reaction completed. The mixture was concentrated and purified by column (PE : EtOAc = 20:1~5:1) to give compound 10a (6.5 g, 63.1%) as a brown solid.
1H NMR DMSO-D6, 400 MHz ^ 12.34 (bs, 1 H), 8.87 (s, 1 H), 7.96 (d, J = 4Hz, 1 H), 7.39 - 7.41 (m, 2 H). Step 8:
Figure imgf000169_0001
To a solution of compound 10a (6.5 g, 0.0237 mol) in 150 ml THF was added NaH (1.14 g, 0.0285 mol) portion wise at 0oC and stirred for 1 hr. Then TIPSCl (5.5 g, 0.0285 mol) was added and stirred at 0oC~20oC for 16 hrs. TLC (PE: EtOAc =5:1) showed the reaction completed. The mixture was extracted with EtOAc (100 mL), washed with 10 ml H2O, dried over Na2SO4, fil- tered, concentrated and purified by column (PE: EtOAc=50:1) to give compound 11a (8.8 g, 86.3) as a yellow oil.
1H NMR CDCl3, 400 MHz ^ 8.54 (s, 1 H), 7.49 (s, 1 H), 7.37~7.39 (m, 2 H), 1.80 (hep, 3 H), 1.16 (d, J=6.8 Hz, 18 H). Step 9:
Figure imgf000169_0002
To a solution of compound 11a (4.3 g, 0.010 mol) in 50 ml THF was added LDA (5 mL, 0.010 mol) drop wise at -65oC under N2 and stirred for 1 hr. Then CBr4 (3.28 g, 0.006 mol) in 10 ml THF was added drop wise and stirred at -60oC~-40oC for 1 h. The mixture was quenched with 1 ml aq. NH4Cl, extracted with EtOAc (20 ml), washed with 10 ml brine, dried over Na2SO4, fil- tered, concentrated and purified by column (PE: EtOAc=100:1) to give compound 12a (1 g, 19.7), compound 12A + 12B (1.16 g, crude) as a yellow oil.
1H NMR CDCl3, 400 MHz Compound-12: ^ 9.13 (bs, 1 H), 7.49 (d, J = 4 Hz, 1 H), 7.36 (d, J = 3 Hz, 1 H), 7.21– 7.24 (m, 1 H). Step 10:
S S
Figure imgf000169_0003
To a stirred solution of compound 12a (0.3 g, 0.003 mol) in DMF (15 ml), Zn(CN)2 (1.77 g, 0.015 mol) was added, Pd2(dba)3 (0.28 g, 0.0003 mol) and xantphos (0.18 g, 0.0003 mol), the reaction mixture was stirred and heated to 120oC for 16 hrs under N2. TLC (PE: EtOAc = 3:1) showed the reaction completed. The mixture was concentrated and purified by column (PE: EtOAc = 20:1~3:1) to give 13a (0.68 g, 75.5%) as a white solid. H NMR CDCl3, 400 MHz 9.24 (bs, 1 H), 7.67 (s, 1H), 7.57 (d, J 5.2 Hz, 1 H), 7.28 (d, J 5.2 Hz, 1 H). Step 11:
Figure imgf000170_0001
To a solution of 13a (0.6 g, 0.002 mol) in 8 ml MeOH was added MeONa (5 ml, 0.010 mol) and heated to 80 oC for 2 h. Then 5 ml 3 N HCl was added and stirred at 20oC for another 16 hrs. LCMS showed the completion of reaction. The mixture was concentrated and purified by prep- HPLC to give 14a (0.3 g, 45.2%) as a white solid.
1H NMR CDCl3, 400 MHz ^ 9.91 (bs, 1 H), 7.63 (s, 1H), 7.54 (d, J=5.2 Hz, 1 H), 7.34 (d, J=5.2 Hz, 1 H), 4.07 (s, 3H). 5) Preparation of 6-[2-(trifluoromethyl)-3-thienyl]-4H-pyrrolo[3,2-d]thiadiazole (Ex.41):
Step 1: 2b 3b To a stirred solution of 2b (15 g, 75 mmol) in DMF (150 mL) was added NIS (25.4 g 112 mmol). The solution was stirred at 25oC for 2 h. TLC (petroleum ether: EtOAc = 3:1, Rf = 0.4) showed the reaction was completed. The reaction was poured into 600 mL water and extracted with (200 mL X 2) EtOAc. The organic layer was washed with H2O (200 mL X 2), sat. Na2SO3 (300 mL) and 200 mL brine, dried over Na2SO4, filtered and concentrated to give the product 3b (22 g, 90% yield) as a yellow solid which was used for the next step without purification.
1H NMR CDCl3: ^ 7.49 (bs, 1 H) 1.50 (s, 9 H) Step 2:
3b
Figure imgf000170_0002
To a suspension of 3b (14 g, 43 mmol) in 450 mL dioxane and 90 mL H2O was added Int 3 (18 g, 91 mol) and Cs2CO3 (42 g, 129 mmol) under N2. Then to the reaction was bubbled with N2 for 30 min and added 2 g Pd(dppf)Cl2 into the reaction. The reaction suspension was stirred for16 hrs at 90oC. TLC (petroleum ether: EtOAc = 3:1, Rf = 0.4) showed the reaction was completed. Then, the reaction was poured into 400 mL ice water and the 2 batches were combined and ex- tracted with EtOAc (400 mL X 2). The organic layer was washed with H2O (300 mL) and brine (300 mL) and then dried over Na2SO4, filtered and concentrated to give the crude product. The crude product was purified by column chromatography eluting with petroleum ether: EtOAc = 5:1 to give the 4b (14 g, 60% yield) as yellow oil.
1H NMR: CDCl3 ^ 9.98 (s, 1 H) 6.20 (d, J = 7.2 Hz 1 H) 6.07 (d, J = 7.2 Hz 1 H) 4.13– 4.15 (m, 3 H) 1.56 (s, 9 H) 1.47 (t, J = 7.2 Hz 3 H). Step 3:
Figure imgf000171_0001
To the solution of 4b (14 g, 51 mmol) in EtOH (150 mL) was added 100 mL 1N HCl at 25oC un- der N2. Then the reaction solution was stirred for 5 hrs at 80oC. TLC (petroleum ether: EtOAc = 2:1, Rf = 0.5) showed the reaction was completed. The reaction was quenched with 500 mL water and extracted with EtOAc (100 mL X 3). The organic layer was washed with 100 mL brine, dried over Na2SO4, filtered and concentrated to give crude product which was purified by column chromatography eluting with petroleum ether: EtOAc = 10:1 to petroleum ether: EtOAc = 3:1 to give the product 5b (2.1 g, 33% yield) as a yellow solid.
1H NMR: CDCl3 ^ 9.02 (s, 1 H) 7.22 -7.24 (m, 1 H) 6.87 (s, 1 H). Step 4:
Figure imgf000171_0002
To a solution of 5b (1.7 g, 14 mmol) in DMF (100 mL) was added KOH (2.67 g, 48 mmol) at 0oC under N2. The reaction mixture was stirred at 0oC for 30 min. Then to the reaction solution was added I2 (6.9 g, 28 mmol) at 0oC. Then the reaction was stirred for 16 hrs at 0oC to 25oC. TLC (petroleum ether : EtOAc = 2:1, Rf = 0.4) showed the reaction was completed. The reaction so- lution was used for the next step without work up. Step 5:
Figure imgf000171_0003
To the reaction solution of 6b (~3.4 g, 13.6 mmol) was added Boc2O (5.93 g, 27.2 mmol) and then TEA (2.75 g, 27.2 mmol) at 25oC. The brown reaction mixture was stirred at 25oC for 2 hrs. TLC (petroleum ether: EtOAc= 10:1, Rf = 0.6) showed the reaction was completed. The reaction solution was quenched with 500 mL H2O and extracted with EtOAc (100 mL X 2). The organic layer was washed with H2O (200 mL) and brine (100 mL) and dried over Na2SO4, con- centrated, purified by column chromatography eluting with petroleum ether to petroleum ether: EtOAc = 20:1 to give 7b (0.6 g, 13% yield for 2 steps) as white solid.
1H NMR: CDCl3 δ7.70 (br s, 1 H) 1.68 (s, 9 H). Step 6:
Figure imgf000172_0001
To a suspension of 7b (200 mg, 0.57 mmol) in toluene (10 mL) was added Int 8B (337 mg, 1.7 mmol) and K2CO3 (393 mg, 2.8 mmol) followed by 50 mg Pd(PPh3)4. The reaction suspension was stirred for 46 hrs at 85oC under N2. TLC (petroleum ether: EtOAc = 10:1, Rf = 0.6) showed the reaction was completed. The reaction was quenched with water (20 mL) and extracted with EtOAc (10 mL). The organic layer was washed with brine (10 mL), dried over Na2SO4, filtered and concentrated to give the crude product which was purified by prep-TLC (petroleum ether: EtOAc = 10:1) to give the product 9b (60 mg 28% yield) as yellow solid. The product was used in the next step without further identification. Step 7:
Figure imgf000172_0002
To a solution of 9b (60 mg, 0.54 mmol) in DCM (10 mL) was added TFA (5 mL). The reaction solution was stirred at 25oC for 16 hrs. TLC (petroleum ether: EtOAc= 2:1, Rf = 0.4, adjusted pH to 10) showed the reaction was completed. The reaction solution was quenched with 20 ml NaHCO3 to adjust pH to 10 and extracted with 10 ml DCM. The organic layer was dried over Na2SO4 and concentrated. The crude product was purified by prep-TLC (petroleum ether:
EtOAc = 2:1) to give 10b (20 mg, 45% yield) as red solid.
1H NMR: Bruker 400 MHz CDCl3 δ 8.96 (bs, 1 H) 8.07– 8.09 (m, 1 H), 7.66 (s, 1 H), 7.57 (d, J = 8 Hz, 1 H). Table P:
Figure imgf000172_0003
L M M l in
Figure imgf000173_0001
II. Biological examples for fungicidal activity
The fungicidal action of the compounds I was demonstrated by the following experiments:
Green House
The spray solutions were prepared in several steps:
The stock solutions were prepared: a mixture of acetone and/or dimethylsulfoxide and the wetting agent/emulsifier Wettol, which is based on ethoxylated alkylphenols, in a relation (volume) sol- vent-emulsifier of 99 to 1 was added to 25 mg of the compound to give a total of 5 ml.
Water was then added to total volume of 100 ml.
This stock solution was diluted with the described solvent-emulsifier-water mixture to the given concentration. 1. Preventative fungicidal control of Botrytis cinerea on leaves of green pepper (Botrci P1)
Young seedlings of green pepper were grown in pots to the 4 to 5 leaf stage. These plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture mentioned in the table below. The next day the plants were inoculated with an aqueous biomalt or solution containing the spore suspension of Botrytis cinerea. Then the plants were immediately transferred to a humid chamber. After 5 days at 22 to 24oC and a relative humidity close to 100 % the extent of fungal attack on the leaves was visually assessed as % diseased leaf area. 2. Preventative fungicidal control of Botrytis cinerea on leaves of green pepper (Botrci P3)
Young seedlings of green pepper were grown in pots to the 4 to 5 leaf stage. These plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture mentioned in the table below. Three days later the plants were inoculated with an aqueous biomalt solution containing the spore suspension of Botrytis cinerea. Then the plants were immediately transferred to a humid chamber. After 5 days at 22 to 24oC and a relative humidity close to 100 % the extent of fungal attack on the leaves was visually assessed as % diseased leaf area. 3. Control of culm rot on pearl millet caused by Fusarium culmorum (Fusacu P1) Pot grown pearl millet seedlings were sprayed to run off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The plants were allowed to air-dry. The next day the plants were inoculated with a spore suspension of Fusarium culmorum in a aqueous biomalt solution. Then the trial plants were immediately transferred to a humid chamber. After 6 days at 23-25oC and a relative humidity close to 100 % the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
4. Control of culm rot on pearl millet caused by Fusarium culmorum (Fusacu P3)
Pot-grown pearl millet seedlings were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The plants were allowed to air-dry. Three days later the plants were inoculated with a spore suspension of Fusarium culmorum in a aqueous biomalt solution. Then the trial plants were immediately transferred to a humid chamber. After 6 days at 23-25oC and a relative humidity close to 100 % the extent of fungal attack on the leaves was visually assessed as % diseased leaf area. 5. Fungicidal control of rice blast caused by Pyricularia oryzae Pyrior P1)
Leaves of pot-grown rice seedlings were sprayed to run-off with an aqueous suspension of the compound prepared as described. The plants were allowed to air-dry. At the following day the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae. Then the trial plants were immediately transferred to a humid chamber. After 6 days at 22-24oC and a relative humidity close to 100 % the extent of fungal attack on the leaves was visually assessed as % diseased leaf area. 6. Preventative fungicidal control of early blight on tomatoes (Alternaria solani) (Alteso P1)
Young seedlings of tomato plants were grown in pots. These plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or mixture mentioned in the table below. The next day, the treated plants were inoculated with an aqueous suspension of Alternaria solani. Then the trial plants were immediately transferred to a humid chamber. After 5 days at 18 to 20° C and a relative humidity close to 100 %, the extent of fungal attack on the leaves was visually assessed as % diseased leaf area. 7. Protective control of soy bean rust on soy beans caused by Phakopsora pachyrhizi (Phakpa P2) Leaves of pot-grown soy bean seedlings were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The plants were allowed to air-dry. The trial plants were cultivated for 2 days in a greenhouse chamber at 23-27oC and a relative humidity between 60 and 80 %. Then the plants were inoculated with spores of Phakopsora pachyrhizi. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber with a relative humidity of about 95 % and 20 to 24o C for 24 h. The trial plants were cultivated for fourteen days in a greenhouse chamber at 23-27oC and a relative humidity between 60 and 80 %. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area. 8. Preventative fungicidal control of apple scrab Venturia inaequalis (Ventin P1)
Young seedlings of apple plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture mentioned in the table below. The next day the plants were inoculated with an aqueous solution containing the spore suspension of Venturia inaequalis. Then the plants were immediately transferred to a humid chamber. After 1 day at 22 to 24・C and a relative humidity close to 100 % the plants were transferred to a chamber with 22-24° C and a relative humidity of 70%. After 12 days the extent of fungal attack on the leaves was visually assessed as % diseased leaf area. 9. Preventative fungicidal control of rape stem rot on soy beans caused by (Sclerotinia sclerotiorum (Sclesc P1 Mycel)
Young seedlings of soy beans were grown in pots. These plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or mixture mentioned in the table below. The next day the treated plants were inoculated with a biomalt suspension, containing the mycel of Sclerotinia sclerotiorum. Then the trial plants were cultivated for 6 days in a greenhouse chamber at 23oC and a relative humidity between 80 and 85%. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area. 10. Preventative fungicidal control of rape stem rot on soy beans caused by (Sclerotinia sclerotiorum (Sclesc P1 Powder)
Young seedlings of soy beans were grown in pots. These plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or mixture mentioned in the table below. The next day the treated plants were inoculated:
Rye and millet grains were infected with Sclerotinia sclerotiorum. After the infection the grains were air dried for a week. The grains were powdered with a mixer.
A small amount of powder was brought onto the soy bean (leaves).
Then the trial plants were cultivated for 7 days in a greenhouse chamber at 23oC and a relative humidity between 80 and 85%.
The extent of fungal attack on the leaves was visually assessed with a classification method: 0, 33, 50, 67 and 100% disease of leaf area and stem. Microtest: The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
1. Activity against the grey mold Botrytis cinerea in the microtiterplate test (Botrci)
The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Botrci cinerea in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. 2. Activity against leaf blotch on wheat caused by Septoria tritici (Septtr)
The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Septoria tritici in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. 3. Activity against rice blast Pyricularia oryzae in the microtiterplate test (Pyrior)
The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Pyricularia oryzae in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. 4. Activity against root rot Fusarium culmorum in the microtiterplate test (Fusacu)
The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Fusarium culmorum in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. The measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free and active compound-free blank value to determine the relative growth in % of the pathogens in the respective active compounds. 5. Activity against stem rot Sclerotinia sclerotiorum in the microtiterplate test (Sclesc)
The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. Sclerotinia sclerotiorum spores (solute with ultra- sonic from a filter membrane) in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.
The measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free and active compound-free blank value to determine the rela- tive growth in % of the pathogens in the respective active compounds.

Claims

Claims: 1.Use of an heteroaryl compound of formula (I),
Figure imgf000177_0001
formula (I)
wherein,
X denotes N;
Y denotes CR5 or N;
A together with the two carbon atoms of pyrrole ring, is selected from the group consist- ing of an unsubstituted or substituted 6-membered aryl; R1 is selected from the group consisting of hydrogen; -(CH2)aOR6; -(CH2)bC(=O)-R7; - C(=O)-(CH2)c-R8; -C(=O)-(CH2)d-OR9; -C(=O)-CR10(=CR11); -C(=O)-(CH2)e-SR12; - (CH2)f-O-C(=O)-R13; -(CH2)g-C(=O)-OR14; -C(=O)-O-(CH2)h-R15; -O-C(=O)-O-(CH2)i- R16; -C(=O)-NR17R18; -C(=S)-NR19R20; -NR21R22; -S(=O)j-R23; -(CH2)k-Si-(R24)l and - (CH2)m-O-(CH2)n-Si-(R25)0; -(CX2)bC(=O)-R25’; C(=O)-(CX2)c-R25’’; -(CHX)bC(=O)-R25’’’ C(=O)-(CHX)c-R25’’’’; wherein X is selected from group consisting of F, Cl, Br and I; R2 is selected from the group consisting of hydrogen; halogen; CN; -C(=O)-OR14; unsub- stituted or substituted alkyl; unsubstituted or substituted cycloalkyl and unsubstituted or substituted cycloalkenyl;
R3 is selected from the group consisting of halogen; CN; -OR6, -C(=O)-OR14, SF5, -C(=O) R7, -C(=O)CF3, -C(=O)CHF2; unsubstituted or substituted alkyl; unsubstituted or sub- stituted heteroalkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloal- kenyl; unsubstituted or substituted heterocycloalkyl; and unsubstituted or substituted heterocycloalkenyl;
R5 is selected from the group consisting of hydrogen; halogen; CN; unsubstituted or sub- stituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted al- kynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloal- kenyl; unsubstituted or substituted heterocycloalkyl and unsubstituted or substituted heterocycloalkenyl;
R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24 and R25, R25’, R25’’, R25’’’, R25’’’’ are independently of each other, selected from the group con- sisting of hydrogen; halogen; hydroxy, CN; unsubstituted or substituted alkyl; unsub- stituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or sub- stituted aryl; unsubstituted or substituted -(alkylene)-aryl; unsubstituted or substituted heterocycloalkyl; unsubstituted or substituted heterocycloalkenyl; unsubstituted or substituted heteroaryl; or R together with R form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substituted;
or R19 together with R20 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein,
the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
or R21 together with R22 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein,
the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
a is 0, 1, 2 or 3; b is 0, 1, 2 or 3; c is 0, 1, 2 or 3; d is 0, 1, 2 or 3; e is 0, 1, 2 or 3; f is 0, 1, 2 or 3; g is 0, 1, 2 or 3; h is 1, 2 or 3; i is 1, 2 or 3; j is 0, 1, 2 or 3; k is 0, 1, 2 or 3; l is 0, 1, 2 or 3; m is 0, 1, 2 or 3; n is 0, 1, 2 or 3; o is 1, 2 or 3;
or each compound in the form of a stereoisomer, an agriculturally acceptable salt, a pro- drug,
a tautomer, an isotopic form, a N-oxide, a S-oxide or a mixture thereof, as an agricultural fungicide. 2. The use of a compound of formula (I) according to claim 1,
wherein, X, Y, R1, R2, R3, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24 and R25, a, b, c, d, e, f, g, h, I, j, k, l, m, n and o are as defined in claim 1;
A together with the two carbon atoms of pyrrole ring, is
Figure imgf000178_0001
wherein,
R71, R72, R73, R74, are independently of each other, selected from the group consisting of H; halogen; CN; -NO2; -NH2; -OH; -SH; oxo; -C(=O)-OR14; -C(=O)-NR17R18; -C(=S)- NR19R20; -N-CN; -S-CN; -O-CN, -CR115(=N-OR116); unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubsti- tuted or substituted heteroalkyl, heteroalkenyl or heteroalkynyl; unsubstituted or sub- stituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substi- tuted heterocycloalkyl, unsubstituted or substituted aryl; unsubstituted or substituted heteroaryl and unsubstituted or substituted heterocycloalkenyl;
R115 and R116 are independently of each other selected from the group consisting of H; hal- ogen; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsub- stituted or substituted alkynyl; unsubstituted or unsubstituted or substituted cycloal- kyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substituted heterocy- cloalkyl; and unsubstituted or substituted heterocycloalkenyl;
and whereby, the alkyl are straight chain or branched, and comprise 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms as chain links;
the alkenyl are straight-chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
the alkynyl are straight-chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
the heteroalkyl, heteroalkenyl and heteroalkynyl comprise 1, 2, 3, 4, 5 or 6 carbon atoms and 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from O, N(H) or S as chain links;
the alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl and heteroalkynyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -OH, -SH, -NH2, -NH(C1-C6)alkyl,-NH-CH(CH3)2, -N(C1-C6-alkyl)2, -N(C1-C6-alkyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, - C(=O)-O-phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -CH2-C(=O)-O-C1-C6-alkyl, - C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -NH-C(=O)C(CH3)3, -S(=O)-C1-C6- alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -NH-SO2-phenyl, - N(CH3)-SO2-phenyl, -C1-C6-alkyl, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phenyl)3, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, oxetanyl, piperidinyl, piperazinyl, mor- pholinyl, thiomorpholinyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, oxadiazolyl, thiadi- azolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; wherein, the alkyl, heterocycloalkyl, cycloalkyl, aryl or heteroaryl are themselves unsubstituted or substi- tuted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl;
the cycloalkyl and cycloalkenyl comprises 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms as ring members;
the heterocycloalkyl and heterocycloalkenyl are 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from the group consisting of O, N(H) and S as ring members;
the cycloalkyl, cycloalkenyl, heterocycloalkyl or heterocycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -C(=O)-H, - C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phenyl, -C(=O)-NH2, - C(=O)-NH(C1-C6)alkyl, -NH-C(=O)C(CH3)3, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2- NH2, -C1-C6-alkyl, -CF3, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, furyl, oxazolyl, thi- azolyl, pyrazolyl, thiophenyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, py- razinyl, phenyl and -CH2-phenyl; wherein the alkyl, cycloalkyl, heterocycloalkyl, aryl or het- eroaryl, are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of F, Cl, Br, I, -CN, -NH2, -CF3, -OH, -SH, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, -OCH3, -O-C2H5, phenyl and -CH2-phenyl;
the aryl are mono-, bicyclic or tricyclic and comprise 6, 10 or 14 carbon atoms; the heteroaryl are mono or bicyclic and 5 or 6 , 7 , 8 , 9 or 10 membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently selected from the group consisting of O, N(H) or S as ring members;
the aryl or heteroaryl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -OH, -SH, -O-CH3, -O-C2H5, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -N(C1-C6-alkyl)2, -N(C1-C6-al- kyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O- phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, - C(=O)-NH-phenyl, -S(=O)-C1-C6-alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -NH-SO2-phenyl, -N(CH3)-SO2-phenyl, -C1-C6-alkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, 1, 2, 4-oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; wherein the alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl. 3. The use of a compound of formula (I) according to claim 1, wherein,
X denotes N and Y denotes CR5; or
X denotes N and Y denotes N;
A is as defined in claim 2; R1 is selected from the group consisting of hydrogen; -CH2-OH; -CH2-OCH3; -CH2-O- CH(CH3)2; -CH2-O-(CH2)2-Si(CH3)3; -C(=O)-CH3; -C(=O)-CH2-CH3; -(C=O)-(CH2)2- CH3; -(C=O)-(CH2)3-CH3; -(C=O)-(CH2)3-CH3; -(C=O)-(CH2)4-CH3; -(C=O)-(CH2)5- CH3; -C(=O)-C(CH3)3; -C(=O)-CH2-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-cyclopropyl; - C(=O)-phenyl; -C(=O)-CH2-cyclopropyl; -C(=O)-CH2-phenyl; -CH2-O-(C=O)-CH3; - CH2-O-(C=O)-CH2-CH3; -CH2-O-(C=O)-(CH2)2-CH3; -CH2-O-(C=O)-(CH2)3-CH3; - CH2-O-(C=O)-(CH2)4-CH3; -CH2-O-(C=O)-(CH2)5-CH3; -CH2-O-(C=O)-C(CH3)3; -CH2- O-(C=O)-phenyl; -C(=O)-OCH3; -C(=O)-OCH2-CH3; -CHF-C(=O)-OCH3; -CHF- C(=O)-OCF3; -CHF-C(=O)-OCH2-CH3; -CHF-C(=O)-OC(CH3)3; -CHF-C(=O)- OCH(CH3)2; -CF2-C(=O)-OCH3; -CF2-C(=O)-OCH2-CH3; -CF2-C(=O)-OC(CH3)3; -CF2- C(=O)-OCH(CH3)2; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4- CH3; -C(=O)-O-(CH2)5-CH3;-C(=O)-O-CH2-CH(CH3)2; -C(=O)-O-CH(CH3)2; -C(=O)-O- CH2-CCl3; -C(=O)-O-C(CH3)3; -C(=O)-O-(CH2)6-CH3; -C(=O)-O-CH2-CH=CH; -C(=O)- O-CH2-C≡CH; -C(=O)O-phenyl; -C(=O)-O-CH2-phenyl; -CH2-C(=O)-OCH3; -CH2- C(=O)-OCH2-CH3; -CH2-C(=O)-O(CH2)2-CH3; -CH2-C(=O)-O(CH2)3-CH3; -CH2-C(=O)- O(CH2)4-CH3; -CH2-C(=O)-O(CH2)5-CH3; -CH2-C(=O)-OC(CH3)3; -CH2-C(=O)-O-CH2- CH=CH; -CH2-C(=O)-O-CH=CH-CH3; -C(=O)-NH2; -C(=O)-NH-CH3; -C(=O)-N- (CH3)2; -C(=O)-pyridyl; -C(=O)-pyrimidinyl; -C(=S)-NH2; -C(=S)-NH-CH3; -C(=S)-N- (CH3)2; -C(=S)-pyridyl; -C(=S)-pyrimidinyl; -S(=O)2-CH3; -S(=O)2-CH2-CH3; -S(=O)2- (CH2)2-CH3; -S(=O)2-(CH2)2-CH3; -S(=O)2-tert butyl; -S(=O)2-phenyl; wherein, cyclo- propyl, phenyl, pyridyl and pyrimidinyl is unsubstituted or substituted with 1, 2 or 3, substituents independently of each other selected from the group consisting of F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -C(=O)-O-CH3; - C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4- CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; methyl, ethyl, propyl, butyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl, tert butyl, cyclopropyl, cyclo- butyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohex- enyl; wherein alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN, - OH, -SH, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -N(C1-C6-alkyl)2, -N(C1-C6-alkyl)-phe- nyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phe- nyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -CH2-C(=O)-O-C1-C6-alkyl, -C(=O)- NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -NH-C(=O)-C(CH3)3, -S(=O)-C1-C6- alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -NH-SO2- phenyl, -N(CH3)-SO2-phenyl, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phenyl)3, phenyl and -CH2-phenyl; wherein, the cycloalkyl or cycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O- C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)- OCH3, -NH-C(=O)-CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R3 is selected from the group consisting of Cl; F; Br; I; CN; -OCH3; -C(=O)-O-CH3; - C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4- CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; SF5, -C(=O)CH3, -C(=O)CF3, -C(=O)CHF2, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, ethynyl, propynyl, butynyl, cyclo- propyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopen- tenyl, cyclohexenyl, oxetanyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, 1,2,4-oxadiazolyl, 1,3,4-trimethyl piperazinyl, 2,3-dihydrofuranyl, 2,3-dihydrothienyl, 2,3-dihydropyrrolyl, 2,3-dihydroisoxazolyl, 1,4-dihydropyridin-1-yl, dihydropyranyl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihy- drooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl and 3,4-dihydrooxazol- 4-yl; wherein, alkyl, alkenyl and alkynyl are independently of each other unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN; -OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -NO2; -NH2; -NH(CH3)2; wherein, the cycloalkyl, cycloalkenyl, heterocycloalkyl and heterocycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, - CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, - C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH-C(=O)-CH3, -NH-C(=O)- C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2- phenyl; R is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; methyl, ethyl, pro pyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, tetrahydro- furanyl, tetrahydrothiophenyl, tetrahydropyranyl, oxetanyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, 1,2,4-oxadiazolyl, 1,3,4-trimethyl piperazinyl, 2,3-dihy- drofuranyl, 2,3-dihydrothienyl, 2,3-dihydropyrrolyl, 2,3-dihydroisoxazolyl, 1,4-dihydro- pyridin-1-yl, dihydropyranyl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihy- drooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl and 3,4-dihydrooxazol-4-yl; wherein, alkyl and alkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2; -CF2-CF3; -C(=O)-O-CH3; -C(=O)-O- CH2-CH3; -NO2; -NH2 and -NH(CH3)2; and wherein, the cycloalkyl, cycloalkenyl, het- erocycloalkyl and heterocycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R71, R72, R73, R74 are independently of each other, selected from the group consisting of H;
Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; oxo; -C(=O)NH2; -CH(=N- OH); -CH(=N-OCH3); -CH(=N-OCH2CH3); -CH(=N-O(CH2)2CH3); -CH(=N- O(CH2)4CH3); ; -N-CN; -S-CN; -O-CN; -C(CH3)(=N-OH); -C(CH3)(=N-OCH3); -C(=O)- O-CH3; -CH=C(CN)2; -O-CH3; -O-CH2-CH3; -O(CH2)2CH3; -O(CH2)3CH3; - O(CH2)4CH3; -O(CH2)5CH3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; iso- pentyl; tert butyl; ethenyl; 1-propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; bu- tynyl; cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cyclopropenyl; cyclobutenyl; cy- clopentenyl; cyclohexenyl; oxetanyl; piperidinyl; piperazinyl; morpholinyl; thiomor- pholinyl; 1,2,4-oxadiazolyl; 1,3,4-trimethyl piperazinyl; 2,3-dihydrofuranyl; 2,3-dihy- drothienyl; 2,3-dihydropyrrolyl; 2,3-dihydroisoxazolyl and 2,3-dihydrooxazol-2-yl; and wherein, alkyl, alkenyl and alkynyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of F, Cl, -CN, -OH, -NH2, -C(=O)-OH, -C(=O)-OCH3, -Si-(CH3)3, -Si-(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phenyl)3, phenyl and - CH2-phenyl; and wherein, the cycloalkyl, cycloalkenyl, heterocycloalkyl and heterocy- cloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other, selected from the group consisting of 1, 2, 3, 4 or 5 substit- uents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH-C(=O)-CH3, -NH-C(=O)- C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2- phenyl. 4. The use of a compound according to claim 1, wherein the compound of formula (I) is a compound of formula I(A), formula I(A)
wherein,
Figure imgf000183_0001
X and Y are as defined as in claim 3;
R1, R2, R3, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R25’, R25’’, R25’’’, R25’’’’, R71, R72, R73 and R74, a, b, c, d, e, f, g, h, I, j, k, l, m, n and o are as defined in claim 2;
or each compound in the form of a stereoisomer, an agriculturally acceptable salt, a prodrug, a tautomer, an isotopic form, a N-oxide or a S-oxide thereof, as an agricultural fungicide. 5. The use of a compound of formula I(A) according to claim 4, wherein, R1 is selected from the group consisting of hydrogen; -CH2-OH; -CH2-OCH3; -CH2-O- CH(CH3)2; -CH2-O-(CH2)2-Si(CH3)3; -C(=O)-CH3; -C(=O)-CH2-CH3; -C(=O)-(CH2)2- CH3; -C(=O)-(CH2)3-CH3; -C(=O)-(CH2)4-CH3; -C(=O)-(CH2)5-CH3;-C(=O)-C(CH3)3; - C(=O)-CH2-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-phenyl; -C(=O)-cyclopropyl; -C(=O)- CH2-cyclopropyl; -C(=O)-CH2-phenyl; -CH2-O-(C=O)-CH3; -CH2-O-(C=O)-CH2-CH3; - CH2-O-(C=O)-(CH2)3-CH3; -CH2-O-(C=O)-(CH2)4-CH3; -CH2-O-(C=O)-(CH2)5-CH3 ; - CH2-O-(C=O)-C(CH3)3; -CH2-O-(C=O)-phenyl; -C(=O)-OCH3; C(=O)-O-(CH2)2CH3; - C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3;-C(=O)-OCH2- CH(CH3)2; -C(=O)-OCH(CH3)2; -C(=O)-O-CH2-CCl3; -C(=O)-OC(CH3)3; -C(=O)-O- (CH2)6-CH3; -C(=O)-O-CH2-CH=CH; -C(=O)-O-CH2-C≡CH; -C(=O)O-phenyl; -C(=O)- O-CH2-phenyl; -CH2-C(=O)-OCH3; -CH2-C(=O)-OCH2-CH3; -CH2-C(=O)-O(CH2)2- CH3; -CH2-C(=O)-O(CH2)3-CH3; -CH2-C(=O)-O(CH2)4-CH3; -CH2-C(=O)-O(CH2)5-CH3; -CH2-C(=O)-OC(CH3)3; -CH2-C(=O)-O-CH2-CH=CH; -CH2-C(=O)-O-CH=CH-CH3; - C(=O)-NH2; -C(=O)-NH-CH3; -C(=O)-N-(CH3 ) 2; -C(=O)-pyridyl; -C(=O)-pyrimidinyl; - C(=S)-NH2; -C(=S)-NH-CH3; -C(=S)-N-(CH3)2; -C(=S)-pyridyl; -C(=S)-pyrimidinyl; - S(=O)2-CH3; -S(=O)2-CH2-CH3; -S(=O)2-(CH2)2-CH3; -S(=O)2-(CH2)2-CH3; -S(=O)2- tertbutyl; -S(=O)2-phenyl; -CHF-C(=O)-OCH3; -CHF-C(=O)-OCF3; -CHF-C(=O)- OCH2-CH3; -CHF-C(=O)-OC(CH3)3; -CHF-C(=O)-OCH(CH3)2; -CF2-C(=O)-OCH3; - CF2-C(=O)-OCH2-CH3; -CF2-C(=O)-OC(CH3)3; -CF2-C(=O)-OCH(CH3)2; wherein, cy- clopropyl, phenyl, pyridyl and pyrimidinyl is unsubstituted or substituted with 1, 2 or 3, substituents independently of each other selected from the group consisting of F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -C(=O)-O-CH3; - C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5- CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; methyl, ethyl, propyl, butyl, hexyl, hep- tyl, isopropyl, isobutyl, isopentyl, tert butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclo- hexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl; wherein alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, F, Br, I, CN, -OH, -SH, -NH2, -NH(C1- C6)alkyl, C( O) H, C( O) C1 C6 alkyl, C( O) OH, C( O) O C1 C6 alkyl, C( O) O phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-O-C1-C6-alkyl, -C(=O)-NH2, -C(=O)-NH(C1- C6)alkyl, -C(=O)-NH-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -CF3, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phenyl)3, phenyl and -CH2-phenyl; wherein, the cycloalkyl or cycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, -CH2- C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH-C(=O)-CH3, -NH- C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R3 is selected from the group consisting of Cl; F; Br; I; CN; -O-CH3; -O-CH2-CH3; -C(=O)- O-CH3; -C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O- (CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; SF5, - C(=O)CH3, -C(=O)CF3, -C(=O)CHF2, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, ethynyl, propynyl, bu- tynyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cy- clopentenyl and cyclohexenyl; wherein, alkyl, alkenyl or alkynyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -NO2; - NH2; -NH(CH3)2; wherein, the cycloalkyl and cycloalkenyl are unsubstituted or substi- tuted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, - C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH- C(=O)-CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; methyl, ethyl, pro- pyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl; wherein, alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of Cl, Br, F, I, CN; -CF3; - CCl3; -CHF2; -CF2-CF3; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -NO2; -NH2; -NH(CH3)2; and wherein, the cycloalkyl and cycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consist- ing of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R71, R72, R73 and R74 are independently of each other, selected from the group consisting of H; Cl; F; Br; I; -CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; -C(=O)NH2; -CH(=N- OH); -CH(=N-OCH3); -CH(=N-OCH2CH3); -CH(=N-O(CH2)2CH3); -CH(=N- O(CH2)4CH3); -C(CH3)(=N-OH); -C(CH3)(=N-OCH3); -C(=O)-O-CH3; -C(=O)-O- (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; - C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1 propenyl; isopropenyl; isobu tenyl; ethynyl; propynyl; butynyl; cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cy- clopropenyl; cyclobutenyl; cyclopentenyl; cyclohexenyl; oxetanyl; piperidinyl; piper- azinyl; morpholinyl; thiomorpholinyl; 1,2,4-oxadiazolyl; 1,3,4-trimethyl piperazinyl; 2,3-dihydrofuranyl; 2,3-dihydrothienyl; 2,3-dihydropyrrolyl; 2,3-dihydroisoxazolyl and 2,3-dihydrooxazol-2-yl; and wherein, alkyl, alkenyl and alkynyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of F, Cl, -CN, -OH, -NH2, -C(=O)-OH, -C(=O)-OCH3, -Si-(CH3)3, -Si-(C2H5)3, -Si-(CH3)2-phe- nyl, -Si-(phenyl)3, phenyl and -CH2-phenyl; and wherein, the cycloalkyl, cycloalkenyl, heterocycloalkyl and heterocycloalkenyl are independently of each other unsubsti- tuted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, - CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH-C(=O)-CH3, - NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl. 6. The use of a compound of formula I(A) according to claim 4 or 5, wherein, R1 is selected from the group consisting of hydrogen; -NH2; -CH2-OH; -CH2-OCH3; -CH2- O-(CH2)2-Si-(CH3)3; -C(=O)-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-O-phenyl; -CHF- C(=O)-OCH3; -CHF-C(=O)-OCF3; -CHF-C(=O)-OCH2-CH3; -CHF-C(=O)-OC(CH3)3; - CHF-C(=O)-OCH(CH3)2; -CF2-C(=O)-OCH3; -CF2-C(=O)-OCH2-CH3; -CF2-C(=O)- OC(CH3)3; -CF2-C(=O)-OCH(CH3)2; -C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)2-CH3; - C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH2- phenyl; -C(=O)-O-CH2-phenyl; -C(=O)-O-CH2-CH=CH; -C(=O)-OC(CH3)3; - CH2C(=O)-OCH3; -S(O)2-phenyl; -S(O)2-CF3; -S-phenyl and -C(=O)-NH2; wherein phenyl is substituted with F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2;
-CF2-CF3; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -C(=O)-O- (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; - C(=O)-O-C(CH3)3; R3 is selected from the group consisting of Cl; F; Br; I; -CN; -O-CH3; -O-CH2-CH3; - C(CH3)2-OH; -CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O- CH(CH3)2; -C(=O)-O-C(CH3)3; SF5, -C(=O)CH3, -C(=O)CF3, -C(=O)CHF2, -CF2-CF3; methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopen- tyl and cyclohexyl; and the R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; -CF3; -CHF2; -CH(F)-CF3; methyl, ethyl, propyl, butyl, pentyl, hexyl, hep- tyl, isopropyl, isobutyl, isopentyl and tert butyl; or R5 is selected from the group consisting of hydrogen, F; Cl; Br; I; CN; -CF3; -CHF2;
-CH(F)-CF3; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, iso- pentyl and tert butyl; and the R3 is selected from the group consisting of Cl; F; Br; I; CN; CF3; O CH3; O CH2 CH3; C(CH3)2 OH; CHF2; CH(F) CF3; CH(CH3)2 OH; CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)- O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CF2-CF3; methyl, ethyl, pro- pyl, butyl, isopropyl, isobutyl, tert butyl, ethenyl, propenyl, butenyl, isopropenyl, iso- butenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclo- hexyl; R71 is selected from the group consisting of hydrogen, -NH2; F ; -NH-CH3; -N(CH3)2 and - NO2; and the remaining of R72, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; - N(CH3)2; -OH; -SH; -C(=O)NH2; -CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); - C(CH3)(=N-OCH3); -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; - C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; - O-CH2-CH3; -CF3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1-propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclo- propyl; and 1,2,4-oxadiazolyl; or R72 is selected from the group consisting of hydrogen, F, Cl, Br and I; and the remain- ing of R71, R73 and R74 are independently of each other selected from the group con- sisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; - C(=O)NH2; -CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); -C(CH3)(=N-OCH3); - C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; - C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; -CF3; me- thyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1- propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; and 1,2,4- oxadiazolyl; or R73 is selected from the group consisting of hydrogen, Cl; F; Br; I; -CN; -NO2; -NH2; - NH-CH3; -N(CH3)2; -C(=O)NH2; -CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); - C(CH3)(=N-OCH3); -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; - C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; - O-CH2-CH3; -CF3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1-propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclo- propyl; and 1,2,4-oxadiazolyl; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; -NH2; -NH-CH3; - N(CH3)2; and -NO2; or R74 is selected from the group consisting of hydrogen, F; -OH; -CN and -OCH3; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; -CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; -C(=O)NH2; -CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); -C(CH3)(=N-OCH3); -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; - C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; -CF3; me- thyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1- propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; and 1,2,4 oxadiazolyl. 7. The use of a compound of formula I(A), according to any one of claims 4 to 6, wherein the compound is: 3-[5-(trifluoromethyl)isothiazol-4-yl]-1H-indole-5-carbonitrile; 3-[3-(trifluoro- methyl)isothiazol-4-yl]-1H-indole-5-carbonitrile; 3-(3,5-dimethylisothiazol-4-yl)-1H-indole-5-car- bonitrile; and 3-(5-methylthiadiazol-4-yl)-1H-indole-5-carbonitrile. 8. The use of a compound according to any one of claims 1 to 3, wherein,
X is N; Y is CR5 or N
A is
Figure imgf000187_0001
R1 is hydrogen; R2 is hydrogen; R3 is selected from the group consisting of Cl; F; Br; I; -CN; -O-CH3; -C(CH3)2-OH; -CH(CH3)- OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)-O-CH3; -CF2-CF3; methyl, ethenyl, iso- propenyl, ethynyl and cyclopropyl; and the R5 is selected from hydrogen; or R5 is hydrogen; and the R3 is selected from the group consisting of Cl; F; Br; I; CN; -CF3;
-O-CH3; -O-CH2-CH3; -C(CH3)2-OH; -CHF2; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O- CH3; -C(=O)-O-C(CH3)3; -CF2-CF3; methyl, tert butyl, ethenyl, isopropenyl, ethynyl and cyclopropyl; R71, R72, R73 and R74 are independently of each other, selected from the group consisting of H; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; oxo; -C(=O)NH2; -CH(=N-OH); - CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -O-CH3; -O(CH2)5CH3; -CF3; methyl; ethynyl; propynyl; butynyl; cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cyclopropenyl; cyclobutenyl; cyclopentenyl; cyclohexenyl; oxetanyl; piperidinyl; piperazinyl; morpholinyl; thiomorpholinyl; 1,2,4-oxadiazolyl. 9. The use of compound of formula (I), according to any one of preceeding claims, wherein, X is N; Y is CH or N
A is:
Figure imgf000187_0002
R1 is hydrogen; R2 is hydrogen; R3 is -CF3; R , R , R and R are independently of each other, selected from the group consisting of hy drogen; Cl; F; Br; I; CN; methyl, ethynyl and propynyl. 10. The compound of formula (I), according to claim 1 or 2, wherein,
X is N; Y is CH or N
A is:
Figure imgf000188_0001
R1 is hydrogen; R2 is hydrogen; R3 is -CHF2 or CH2F;
R71, R72, R73 and R74 are independently of each other, selected from the group consisting of hy- drogen; Cl; F; Br; I; CN; methyl, ethynyl and propynyl. 11. A heteroaryl compound of formula (I),
Figure imgf000188_0002
formula (I)
wherein,
X denotes N; Y denotes CR5 or N;
A together with the two carbon atoms of pyrrole ring, is
Figure imgf000188_0003
R1 is selected from the group consisting of hydrogen; -(CH2)aOR6; -(CH2)bC(=O)-R7; - C(=O)-(CH2)c-R8; -C(=O)-(CH2)d-OR9; -C(=O)-CR10(=CR11); -C(=O)-(CH2)e-SR12; - (CH2)f-O-C(=O)-R13; -(CH2)g-C(=O)-OR14; -C(=O)-O-(CH2)h-R15; -O-C(=O)-O-(CH2)i- R16; -C(=O)-NR17R18; -C(=S)-NR19R20; -NR21R22; -S(=O)j-R23; -(CH2)k-Si-(R24)l and - (CH2)m-O-(CH2)n-Si-(R25)0; -(CX2)bC(=O)-R25’; C(=O)-(CX2)c-R25’’; -(CHX)bC(=O)-R25’’’ C(=O)-(CHX)c-R25’’’’; wherein X is selected from group consisting of F, Cl, Br and I; R2 is selected from the group consisting of hydrogen; halogen; CN; -C(=O)-OR14; unsub- stituted or substituted alkyl; unsubstituted or substituted cycloalkyl and unsubstituted or substituted cycloalkenyl;
R3 is selected from the group consisting of halogen; CN; -OR6, -C(=O)-OR14, SF5, -C(=O) R7, -C(=O)CF3, -C(=O)CHF2; unsubstituted or substituted alkyl; unsubstituted or sub- stituted heteroalkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloal kenyl; unsubstituted or substituted heterocycloalkyl; and unsubstituted or substituted heterocycloalkenyl;
R5 is selected from the group consisting of hydrogen; halogen; CN; unsubstituted or sub- stituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted al- kynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloal- kenyl; unsubstituted or substituted heterocycloalkyl and unsubstituted or substituted heterocycloalkenyl;
R6, R7, R8, R9, R10, R11, R12, R13, R15, R16, R17, R18, R19, R20, R21, R22, R23, R25, R25’, R25’’, R25’’’ and R25’’’’ are independently of each other, selected from the group consisting of hy- drogen; halogen; hydroxy, CN; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substituted aryl; unsubstituted or substituted -(alkylene)-aryl; unsubstituted or substituted heterocyclo- alkyl; unsubstituted or substituted heterocycloalkenyl; unsubstituted or substituted heteroaryl;
R14 is selected from the group consisting of halogen; CN; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; un- substituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsub- stituted or substituted aryl; unsubstituted or substituted -(alkylene)-aryl; unsubstituted or substituted heterocycloalkyl; unsubstituted or substituted heterocycloalkenyl; un- substituted or substituted heteroaryl;
or R17 together with R18 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substituted;
or R19 together with R20 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein,
the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substi- tuted;
or R21 together with R22 form a heterocycloalkyl, heterocycloalkenyl or a heteroaryl; wherein, the heterocycloalkyl, heterocycloalkenyl or a heteroaryl is unsubstituted or substituted;
R71, R72, R73 and R74 are independently of each other, selected from the group consisting of H; halogen; CN; -NO2; -NH2; -OH; -SH; oxo; -(CH2)g-C(=O)-OR14; -C(=O)-NR17R18; - C(=S)-NR19R20; -N-CN; -S-CN; -O-CN, -CR115(=N-OR116); unsubstituted or substi- tuted alkyl; unsubstituted or substituted alkenyl; unsubstituted or substituted alkynyl; unsubstituted or substituted heteroalkyl, heteroalkenyl or heteroalkynyl; unsubsti- tuted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubsti- tuted or substituted heterocycloalkyl and unsubstituted or substituted heterocycloal- kenyl;
R115 and R116 are independently of each other selected from the group consisting of H; halo- gen; unsubstituted or substituted alkyl; unsubstituted or substituted alkenyl; unsubsti- tuted or substituted alkynyl; unsubstituted or unsubstituted or substituted cycloalkyl; unsubstituted or substituted cycloalkenyl; unsubstituted or substituted heterocycloal kyl; and unsubstituted or substituted heterocycloalkenyl;
and whereby,
if not specified otherwise, the alkyl are straight-chain or branched, and comprise 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms as chain links;
the alkenyl are straight-chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
the alkynyl are straight-chain or branched, and comprise 2, 3, 4, 5 or 6 carbon atoms as chain links;
the heteroalkyl, heteroalkenyl and heteroalkynyl comprise 1, 2, 3, 4, 5 or 6 carbon atoms and 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from O, N(H) or S as chain links;
if not specified otherwise, the alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl and heteroal- kynyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -OH, -SH, -NH2, -NH(C1-C6)alkyl, -NH- CH(CH3)2, -N(C1-C6-alkyl)2, -N(C1-C6-alkyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)- OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, - CH2-C(=O)-O-C1-C6-alkyl, -C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -NH- C(=O)C(CH3)3, -S(=O)-C1-C6-alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, - S(=O)2-NH2, -NH-SO2-phenyl, -N(CH3)-SO2-phenyl, -C1-C6-alkyl, -Si-(CH3)3, -Si(C2H5)3, -Si- (CH3)2-phenyl, -Si-(phenyl)3, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, oxetanyl, pi- peridinyl, piperazinyl, thiomorpholinyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, oxadi- azolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; wherein, the alkyl, heterocycloalkyl, cycloalkyl, aryl or heteroaryl are themselves unsubsti- tuted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O- C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; the cycloalkyl and cycloalkenyl comprises 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms as ring members;
the heterocycloalkyl and heterocycloalkenyl are 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently of each other selected from the group consisting of O, N(H) and S as ring members;
the cycloalkyl, cycloalkenyl, heterocycloalkyl or heterocycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -C(=O)-H, - C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phenyl, -C(=O)-NH2, - C(=O)-NH(C1-C6)alkyl, -NH-C(=O)C(CH3)3, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2- NH2, -C1-C6-alkyl, -CF3, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, furyl, oxazolyl, thi- azolyl, pyrazolyl, thiophenyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, py- razinyl, phenyl and -CH2-phenyl; wherein the alkyl, cycloalkyl, heterocycloalkyl, aryl or het- eroaryl, are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of F, Cl, Br, I, -CN, -NH2, -CF3, -OH, -SH, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, -OCH3, -O-C2H5, phenyl and -CH2-phenyl; the aryl are mono , bicyclic or tricyclic and comprise 6, 10 or 14 carbon atoms; the heteroaryl are mono- or bicyclic and 5- or 6-, 7-, 8-, 9- or 10- membered and comprise 1, 2, 3, 4 or 5 heteroatoms independently selected from the group consisting of O, N(H) or S as ring members;
the aryl or heteroaryl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of F, Cl, Br, I, -NO2, -CN, -OH, -SH, -O-CH3, -O-C2H5, -NH2, -NH(C1-C6)alkyl, -NH-CH(CH3)2, -N(C1-C6-alkyl)2, -N(C1-C6-al- kyl)-phenyl, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O- phenyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -C(=O)-NH2, -C(=O)-NH(C1-C6)alkyl, - C(=O)-NH-phenyl, -S(=O)-C1-C6-alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -NH-SO2-phenyl, -N(CH3)-SO2-phenyl, -C1-C6-alkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, furyl, oxazolyl, thiazolyl, pyrazolyl, thiophenyl, 1, 2, 4-oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperazinyl, pyrazinyl, phenyl and -CH2-phenyl; wherein the alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl a is 0, 1, 2 or 3; b is 0, 1, 2 or 3; c is 0, 1, 2 or 3; d is 0, 1, 2 or 3; e is 0, 1, 2 or 3; f is 0, 1, 2 or 3; g is 0, 1, 2 or 3; h is 1, 2 or 3; I is 1, 2 or 3; j is 0, 1, 2 or 3; k is 0, 1, 2 or 3; l is 0, 1, 2 or 3; m is 0, 1, 2 or 3; n is 0, 1, 2 or 3; o is 1, 2 or 3; or each compound in the form of a stereoisomer, an agriculturally acceptable salt, a prodrug, a tautomer, an isotopic form, a N-oxide, a S-oxide or a mixture thereof. 12. A compound of formula (I) according to claim 11, wherein,
X denotes N and Y denotes CR5; or
X denotes N and Y denotes N;
A is as defined in claim 11; R1 is selected from the group consisting of hydrogen; -CH2-OH; -CH2-OCH3; -CH2-O- CH(CH3)2; -CH2-O-(CH2)2-Si(CH3)3; -C(=O)-CH3; -C(=O)-CH2-CH3; -(C=O)-(CH2)2- CH3; -(C=O)-(CH2)3-CH3; -(C=O)-(CH2)3-CH3; -(C=O)-(CH2)4-CH3; -(C=O)-(CH2)5- CH3; -C(=O)-C(CH3)3; -C(=O)-CH2-OCH3; -C(=O)-CH=CH-CH3; -C(=O)-cyclopropyl; - C(=O)-phenyl; -C(=O)-CH2-CH3; -C(=O)-(CH2)2-CH3; -C(=O)-(CH2)3-CH3; -C(=O)- (CH2)4-CH3; -C(=O)-(CH2)5-CH3; -C(=O)-CH2-cyclopropyl; -C(=O)-CH2-phenyl; -CH2- O-(C=O)-CH3; -CH2-O-(C=O)-CH2-CH3; -CH2-O-(C=O)-(CH2)3-CH3; -CH2-O-(C=O)- (CH2)4-CH3; -CH2-O-(C=O)-(CH2)5-CH3 ; -CH2-O-(C=O)-C(CH3)3; -CH2-O-(C=O)-phe- nyl; -C(=O)-OCH3; C(=O)-O-(CH2)2CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3;-C(=O)-OCH2-CH(CH3)2; -C(=O)-OCH(CH3)2; -C(=O)-O-CH2- CCl3; -C(=O)-OC(CH3)3; -C(=O)-O-(CH2)6-CH3; -C(=O)-O-CH2-CH=CH; -C(=O)-O- CH2-C≡CH; -C(=O)O-phenyl; -C(=O)-O-CH2-phenyl; -CH2-C(=O)-OCH3; -CH2-C(=O)- OCH2-CH3; -CH2-C(=O)-O-(CH2)2-CH3; -CH2-C(=O)-O-(CH2)3-CH3; -CH2-C(=O)-O- (CH2)4-CH3; -CH2-C(=O)-O-(CH2)5-CH3; -CH2-C(=O)-OC(CH3)3; -CH2-C(=O)-O-CH2- CH CH; CH2 C( O) O CH CH CH3; C( O) NH2; C( O) NH CH3; C( O) N (CH3)2; -C(=O)-pyridyl; -C(=O)-pyrimidinyl; -C(=S)-NH2; -C(=S)-NH-CH3; -C(=S)-N- (CH3 ) 2; -C(=S)-pyridyl; -C(=S)-pyrimidinyl; -S(=O)2-CH3; -S(=O)2-CH2-CH3; -S(=O)2- (CH2)2-CH3; -S(=O)2-(CH2)2-CH3; -S(=O)2-tertbutyl; -S(=O)2-phenyl; wherein, cyclo- propyl, phenyl, pyridyl and pyrimidinyl is unsubstituted or substituted with 1, 2 or 3, substituents independently of each other selected from the group consisting of F, Cl, Br, I, methyl, ethyl, propyl, butyl, isopropyl, isobutyl and -NO2; R2 is selected from the group consisting of hydrogen; Cl, Br, F, I, CN; -C(=O)-O-CH3; - C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4- CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH-(CH3)2; -C(=O)-O-C(CH3)3; methyl, ethyl, propyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl, tert butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl; wherein alkyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents inde- pendently of each other selected from the group consisting of Cl, Br, F, I, CN, -OH, - SH, -C(=O)-H, -C(=O)-C1-C6-alkyl, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C(=O)-O-phe- nyl, -CH2-C(=O)-OH, -CH2-C(=O)-C1-C6-alkyl, -CH2-C(=O)-O-C1-C6-alkyl, -C(=O)- NH2, -C(=O)-NH(C1-C6)alkyl, -C(=O)-NH-phenyl, -NH-C(=O)-C(CH3)3, -S(=O)-C1-C6- alkyl, -S(=O)-phenyl, -S(=O)2-C1-C6-alkyl, -S(=O)2-phenyl, -S(=O)2-NH2, -NH-SO2- phenyl, -N(CH3)-SO2-phenyl, -CF3, -Si-(CH3)3, -Si(C2H5)3, -Si-(CH3)2-phenyl, -Si-(phe- nyl)3, phenyl and -CH2-phenyl; wherein, the cycloalkyl or cycloalkenyl are unsubsti- tuted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, se- lected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, - O-CH3, -O-C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2- C(=O)-OCH3, -NH-C(=O)-CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R3 is selected from the group consisting of Cl; F; Br; I; CN; -OCH3; -C(=O)-O-CH3; - C(=O)-O-CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4- CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, oxetanyl, piperidinyl, piper- azinyl, morpholinyl, thiomorpholinyl, 1,2,4-oxadiazolyl, 1,3,4-trimethyl piperazinyl, 2,3-dihydrofuranyl, 2,3-dihydrothienyl, 2,3-dihydropyrrolyl, 2,3-dihydroisoxazolyl, 1,4- dihydropyridin-1-yl, dihydropyranyl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihy- drooxazol-3-yl and 3,4-dihydrooxazol-4-yl; wherein, alkyl, alkenyl and alkynyl are in- dependently of each other unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN; - OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -NO2; -NH2; -NH(CH3)2; wherein, the cyclo- alkyl, cycloalkenyl, heterocycloalkyl and heterocycloalkenyl are unsubstituted or sub- stituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)-OCH3, -NH- C( O) CH3, NH C( O) C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; methyl, ethyl, pro- pyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, tetrahydro- furanyl, tetrahydrothiophenyl, tetrahydropyranyl, oxetanyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, 1,2,4-oxadiazolyl, 1,3,4-trimethyl piperazinyl, 2,3-dihy- drofuranyl, 2,3-dihydrothienyl, 2,3-dihydropyrrolyl, 2,3-dihydroisoxazolyl, 1,4-dihydro- pyridin-1-yl, dihydropyranyl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihy- drooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl and 3,4-dihydrooxazol-4-yl; wherein, alkyl and alkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other selected from the group consisting of Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2; -CF2-CF3; -C(=O)-O-CH3; -C(=O)-O- CH2-CH3; -NO2; -NH2 and -NH(CH3)2; and wherein, the cycloalkyl, cycloalkenyl, het- erocycloalkyl and heterocycloalkenyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O-C2H5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl; R71, R72, R73 and R74, are independently of each other, selected from the group consisting of H; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; oxo; -C(=O)NH2; - CH(=N-OH); -CH(=N-OCH3); -CH(=N-OCH2CH3); -CH(=N-O(CH2)2CH3); -CH(=N- O(CH2)4CH3); -C(CH3)(=N-OH); -C(CH3)(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -O- CH3; -O-CH2-CH3; -O(CH2)2CH3; -O(CH2)3CH3; -O(CH2)4CH3; -O(CH2)5CH3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1-propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; cyclobutyl; cyclopen- tyl; cyclopropenyl; cyclobutenyl; cyclopentenyl; cyclohexenyl; oxetanyl; piperidinyl; pi- perazinyl; morpholinyl; thiomorpholinyl; 1,2,4-oxadiazolyl; 1,3,4-trimethyl piperazinyl; 2,3-dihydrofuranyl; 2,3-dihydrothienyl; 2,3-dihydropyrrolyl; 2,3-dihydroisoxazolyl and 2,3-dihydrooxazol-2-yl; and wherein, alkyl, alkenyl and alkynyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents selected from the group consisting of F, Cl, -CN, -OH, -NH2, -C(=O)-OH, -C(=O)-OCH3, -Si-(CH3)3, -Si-(C2H5)3, -Si-(CH3)2-phe- nyl, -Si-(phenyl)3, phenyl and -CH2-phenyl; and wherein, the cycloalkyl, cycloalkenyl, heterocycloalkyl and heterocycloalkenyl are themselves unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of 1, 2, 3, 4 or 5 substituents independently of each other, selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OH, -NH2, -O-CF3, -SH, -O-CH3, -O- C2H5, -C(=O)-CH3, -CH2-C(=O)-OH, -C(=O)-OH, -C(=O)-O-phenyl, -CH2-C(=O)- OCH3, -NH-C(=O)-CH3, -NH-C(=O)-C(CH3)3, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl, phenyl and -CH2-phenyl. 13. A compound according to claim 11, wherein the compound of formula (I) is a compound of formula I(A), formula I(A)
wherein,
Figure imgf000194_0001
X and Y are as defined in claim 9;
R1, R2, R3, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R25, R71, R72, R73 and R74, a, b, c, d, e, f, g, h, I, j, k, l, m, n and o are as defined in claim 9; or each compound in the form of a stereoisomer, an agriculturally acceptable salt, a prodrug, a tautomer, an isotopic form, a N-oxide or a S-oxide thereof. 14. A compound of formula I(A) according to claim 11, wherein, R1, R2, R3, R5, R71, R72, R73 and R74 are as in claim 5. 15. The compound of formula I(A) according to claim 13 or 14, wherein, R1 is selected from the group consisting of hydrogen, -NH2; -CH2-OH; -CH2-OCH3; -CH2- O-(CH2)2-Si-(CH3)3; -C(=O)-OCH3; -C(=O)-CH=CH-CH3; -C(=O)O-phenyl; -C(=O)-O- CH2-CH3; -C(=O)-O-(CH2)2-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; - C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH2-phenyl; -C(=O)-O-CH2-phenyl; -C(=O)-O-CH2- CH=CH; -C(=O)-OC(CH3)3; -CH2C(=O)-OCH3; -S(O)2-phenyl; -S(O)2-CF3; -S-phenyl and -C(=O)-NH2; wherein phenyl is substituted with F, Cl, Br, I and -NO2; R2 is selected from the group consisting of hydrogen, Cl, Br, F, I, CN; -CF3; -CCl3; -CHF2;
-CF2-CF3; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-CH2-CH3; -C(=O)-O- (CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; - C(=O)-O-C(CH3)3; R3 is selected from the group consisting of Cl; F; Br; I; -CN; -O-CH3; -O-CH2-CH3; - C(CH3)2-OH; -CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O- CH(CH3)2; -C(=O)-O-C(CH3)3; -CF2-CF3; methyl, ethyl, propyl, butyl, isopropyl, isobu- tyl, tert butyl, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; and the R5 is selected from the group consisting of hydrogen; F; Cl; Br; I; CN; -CF3; -CHF2; -CH(F)-CF3; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl and tert butyl; or R5 is selected from the group consisting of F; Cl; Br; I; CN; -CF3; -CHF2; -CH(F)- CF3; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl and tert butyl; and the R3 is independently of each other is selected from the group consisting of Cl; F; Br; I; CN; -CF3; -O-CH3; -O-CH2-CH3; -C(CH3)2-OH; -CHF2; -CH(F)- CF3; -CH(CH3)2-OH; -CH(CF3)-OH; -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O- (CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CF2- CF3; methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert butyl, ethenyl, propenyl, bu tenyl, isopropenyl, isobutenyl, ethynyl, propynyl, butynyl, cyclopropyl, cyclobutyl, cy- clopentyl and cyclohexyl; R71 is selected from the group consisting of -NH2; F ; -NH-CH3; -N(CH3)2 and -NO2; and the remaining of R72, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; - SH; -C(=O)NH2; -CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); -C(CH3)(=N-OCH3); -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; - C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; -CF3; me- thyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1- propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; and 1,2,4- oxadiazolyl; or R72 is selected from the group consisting of F, Cl, Br and I; and the remaining of R71, R73 and R74 are independently of each other selected from the group consisting of hydrogen; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; -C(=O)NH2; - CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); -C(CH3)(=N-OCH3); -C(=O)-O-CH3; - C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; -C(=O)-O- CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; -CF3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1-propenyl; iso- propenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; and 1,2,4-oxadiazolyl; or R73 is selected from the group consisting of Cl; F; Br; I; -CN; -NO2; -NH2; -NH-CH3; - N(CH3)2; -C(=O)NH2; -CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); -C(CH3)(=N- OCH3); -C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O- (CH2)5-CH3; -C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; -O-CH2- CH3; -CF3; methyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1-propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; and 1,2,4-oxadiazolyl; and the remaining of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; -NH2; -NH-CH3; - N(CH3)2; and -NO2; or R74 is selected from the group consisting of F; -OH; -CN and -OCH3; and the remain- ing of R71, R72 and R73 are independently of each other is selected from the group consisting of hydrogen; Cl; F; Br; I; -CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; - C(=O)NH2; -CH(=N-OH); -C(CH3)(=N-OH); -CH(=N-OCH3); -C(CH3)(=N-OCH3); - C(=O)-O-CH3; -C(=O)-O-(CH2)3-CH3; -C(=O)-O-(CH2)4-CH3; -C(=O)-O-(CH2)5-CH3; - C(=O)-O-CH(CH3)2; -C(=O)-O-C(CH3)3; -CH=C(CN)2; -OCH3; -O-CH2-CH3; -CF3; me- thyl; ethyl; propyl; isopropyl; butyl; isobutyl; pentyl; isopentyl; tert butyl; ethenyl; 1- propenyl; isopropenyl; isobutenyl; ethynyl; propynyl; butynyl; cyclopropyl; and 1,2,4- oxadiazolyl. 16. The compound of formula (I), according to claim 11, wherein,
X is N; Y is CR5 or N A is selected from the group consisting of:
Figure imgf000196_0001
R1 is hydrogen; R2 is hydrogen; R3 is selected from the group consisting of Cl; F; Br; I; -CN;
-O-CH3; -C(CH3)2-OH; -CH(CH3)-OH; -CF3; -CH(CF3)-OH; -CHF2; -CH(F)-CF3; - C(=O)-O-CH3; -CF2-CF3; methyl, ethenyl, isopropenyl, ethynyl and cyclopropyl; and the R5 is hydrogen; or R5 is hydrogen; and the R3 is selected from the group consisting of Cl; F; Br; I; CN; -CF3; -O- CH3; -O-CH2-CH3; -C(CH3)2-OH; -CHF2; -CH(F)-CF3; -CH(CF3)-OH; -C(=O)-O-CH3; - C(=O)-O-C(CH3)3; -CF2-CF3; methyl, tert butyl, ethenyl, isopropenyl, ethynyl and cy- clopropyl; R71, R72, R73 and R74 are independently of each other, selected from the group consisting of H; Cl; F; Br; I; CN; -NO2; -NH2; -NH-CH3; -N(CH3)2; -OH; -SH; oxo; -C(=O)NH2; -CH(=N-OH); - CH(=N-OCH3); -C(=O)-O-CH3; -CH=C(CN)2; -O-CH3; -O(CH2)5CH3; -CF3; methyl; ethynyl; propynyl; butynyl; cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cyclopropenyl; cyclobutenyl; cyclopentenyl; cyclohexenyl; oxetanyl; piperidinyl; piperazinyl; morpholinyl; thiomorpholinyl; 1,2,4-oxadiazolyl. 17. The compound of formula I(A), according to any one of claims 12 to 16, wherein the compound is: 3-[5-(trifluoromethyl)isothiazol-4-yl]-1H-indole-5-carbonitrile; 3-[3-(trifluoro- methyl)isothiazol-4-yl]-1H-indole-5-carbonitrile; 3-(3,5-dimethylisothiazol-4-yl)-1H-indole-5-car- bonitrile; and 3-(5-methylthiadiazol-4-yl)-1H-indole-5-carbonitrile. 18. The compound of formula (I), according to claim 11, wherein,
X is N; Y is CH or N
A is:
Figure imgf000196_0002
R1 is hydrogen; R2 is hydrogen; R3 is -CF3;
R71, R72, R73 and R74 are independently of each other, selected from the group consisting of hy- drogen; Cl; F; Br; I; CN; methyl, ethynyl, propynyl. 19. The compound of formula (I), according to claim 11, wherein,
X is N; Y is CH or N
A is:
Figure imgf000197_0001
R1 is hydrogen; R2 is hydrogen; R3 is -CHF2 or CH2F;
R71, R72, R73 and R74 are independently of each other, selected from the group consisting of hy- drogen; Cl; F; Br; I; CN; methyl, ethynyl, propynyl. 20. An agrochemical mixture comprising at least one compound according to any one of claims 11 to 19, or as defined in claims 1 to10, or in the form of a stereoisomer or an agricultur- ally acceptable salt or a tautomer or an isotopic form or a N-oxide or a S-oxide or a prodrug thereof, and at least one pesticidally active substance selected from the group consisting of herbicides, safeners, fungicides, insecticides and plant growth regulators. 21. A composition comprising at least one compound according to any one of claims 11 to 19, or as defined in claims 1 to 10, or in the form of a stereoisomer or an agriculturally acceptable salt or a tautomer or an isotopic form of a N-oxide or a S-oxide or a prodrug thereof, and an auxiliary. 22. A method for combating phytopathogenic harmful fungi, which process comprises treating the phytopathogenic fungi, the plant, or the plant propagation material selected from seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seed- lings and young plants to be protected against fungal attack, the stored materials or harvest, or alternately, the locus or soil or soil substituents or surfaces therefrom, with an effective amount of at least one compound of formula (I), according to any one of claims 11 to 19, or as defined in claims 1 to 10, an agriculturally acceptable salt thereof or a tautomer or an isotopic form or a N-oxide or a S-oxide or a prodrug.
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