WO2019122320A1 - Benzosultames hétérocycliques et analogues - Google Patents

Benzosultames hétérocycliques et analogues Download PDF

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Publication number
WO2019122320A1
WO2019122320A1 PCT/EP2018/086551 EP2018086551W WO2019122320A1 WO 2019122320 A1 WO2019122320 A1 WO 2019122320A1 EP 2018086551 W EP2018086551 W EP 2018086551W WO 2019122320 A1 WO2019122320 A1 WO 2019122320A1
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unsubstituted
substituted
alkyl
halogen atoms
different
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PCT/EP2018/086551
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English (en)
Inventor
Philippe Desbordes
Jérémy DUFOUR
Mathieu Gourgues
Virginie LEMPEREUR
Dominique Loque
Sébastien NAUD
Vincent Thomas
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Bayer Aktiengesellschaft
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Publication of WO2019122320A1 publication Critical patent/WO2019122320A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—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 disclosure relates to fungicidal active compounds, more specifically to heterocyclic benzosultams and analogues thereof, processes and intermediates for their preparation and use thereof as fungicidal active compounds, particularly in the form of fungicide compositions.
  • the present disclosure also relates to methods for the control of phytopathogenic fungi using these compounds or compositions comprising thereof.
  • Nitrogen-containing heterocyclic compounds are known to be useful as crop protection agents to combat or prevent microorganisms’ infestations.
  • JP2014/221747 and JP2008/088139 disclose substituted quinoline derivatives that may be used as fungicides.
  • JP 2017/001998 discloses further substituted quinoline derivatives that may be used as fungicides.
  • JP 2017/001998 discloses compounds having a 1 ,4-benzothiazine-1 ,3-dione or -1 , 1 ,3-trione ring bonded to the 3-position of the quinoline ring.
  • fungicidal agents Numerous fungicidal agents have been developed until now. However, the need remains for the development of new fungicidal compounds as such, so as to provide compounds being effective against a broad spectrum of fungi, having lower toxicity, higher selectivity, being used at lower dosage rate to reduce or avoid unfavorable environmental or toxicological effects whilst still allowing effective pest control. It may also be desired to have new compounds to prevent the emergence of fungicides resistances.
  • the present invention provides new fungicidal compounds which have advantages over known compounds and compositions in at least some of these aspects.
  • the invention relates to compounds of formula (I) as recited in the claims and as disclosed herein, to compositions comprising thereof, to their use as fungicide and to processes for making them.
  • the present invention provides heterocyclic benzosultams and analogues thereof as described herein below that may be used as microbicide, preferably as fungicide.
  • the present invention provides compounds of formula (I)
  • A is a 5- or 6-nnennbered unsaturated heterocyclyl ring comprising 1 , 2 or 3 heteroatoms independently selected in the list consisting of N, O and S ;
  • Z is selected from the group consisting of hydrogen atom, halogen atom, Ci-Cs-alkyl, C-i-Cs- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, C2-Cs-alkenyl, C2-C8-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different, C2-C8- alkynyl, C2-C8-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different, C3-C7-cycloalkyl, C 4 -C7-cycloalkenyl, hydroxyl, C-i-Cs-alkoxy, C-i-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, aryl, heterocyclyl, formyl, C-i-Cs-alkylcarbonyl, (hydroxyimino)Ci-
  • n 0, 1 , 2 or 3 ;
  • X is independently selected from the group consisting of halogen atom, C-i-Cs-alkyl, C-i-Cs- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, C2-Cs-alkenyl, C2-C8-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different, C2-C8- alkynyl, C2-C8-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different, C3-C7-cycloalkyl, C3-C7-halogenocycloalkyl comprising up to 9 halogen atoms that can be the same or different, C3-C7-cycloalkyl-Ci-C8-alkyl, C 4 -C7-cycloalkenyl, hydroxyl, C-i-Cs-alkoxy, C-i-Cs- halogenoalk
  • Y 1 is selected from the group consisting of hydrogen atom, halogen atom, Ci-Cs-alkyl, C1- C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, C2- Cs-alkenyl, C2-Cs-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different, C2-Cs-alkynyl, C2-Cs-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different, C3-C7-cycloalkyl, C 4 -C7-cycloalkenyl, hydroxyl, C-i-Cs-alkoxy, Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, aryl, heterocyclyl, formyl, C-i-Cs-alkylcarbonyl, (hydroxyimino)Ci-C8
  • Y 2 , Y 3 , Y 4 and Y 5 are independently selected from the group consisting of hydrogen atom, halogen atom, Ci-C8-alkyl, C-i-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, C2-Cs-alkenyl, C2-C8-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different, C2-Cs-alkynyl, C2-C8-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different, C3-C7-cycloalkyl, C 4 -C7-cycloalkenyl, hydroxyl, C-i-Cs-alkoxy, C-i-Cs- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, aryl, heterocyclyl, formyl, C-i-Cs
  • R 1a and R 1 b are independently selected from the group consisting of hydrogen atom, halogen atom, Ci-Cs-alkyl, Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, C2-Cs-alkenyl, C2-C8-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different, C2-Cs-alkynyl, C2-Cs-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different, C3-C7-cycloalkyl, C3-C7- halogenocycloalkyl comprising up to 9 halogen atoms that can be the same or different, C3-C7-cycloalkyl-Ci-C8-alkyl, aryl, aryl-Ci-Cs-alkyl, heterocyclyl, heterocyclyl-Ci-Cs-alky
  • R 1a and R 1b together with the carbon atom to which they are linked form an unsubstituted or substituted methylidene group ;
  • R 2a and R 2b are independently selected from the group consisting of hydrogen atom, halogen atom, C-i-Cs-alkyl, C-i-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, C2-Cs-alkenyl, C2-C8-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different, C2-Cs-alkynyl, C2-Cs-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different, C3-C7-cycloalkyl, C3-C7- halogenocycloalkyl comprising up to 9 halogen atoms that can be the same or different, C3-C7-cycloalkyl-Ci-C8-alkyl, aryl, aryl-C-i-Cs-alkyl, heterocyclyl, heterocyclyl-C-i-
  • R 2a and R 2b together with the carbon atom to which they are linked form an unsubstituted or substituted 3-, 4-, 5- or 6-membered, saturated or partially saturated, carbocycle or heterocycle comprising at least 1 heteroatom selected in the list consisting of N,0 and S, or
  • variable e.g. X, Y 1 , Y 2 , Y 3 , Y 4 , Y 5 or Z
  • X e.g. X, Y 1 , Y 2 , Y 3 , Y 4 , Y 5 or Z
  • the variable may be substituted with one or more substituents that may be identical or different.
  • the expression“one or more substituents” refers to a number of substituents that ranges from one to the maximum number of substituents possible based on the number of available bonding sites, provided that the conditions of stability and chemical feasibility are met.
  • the one or more substituents of the substituted variable may be independently selected from the group consisting of halogen atom, nitro, hydroxyl, cyano, amino, sulfanyl, pentafluoro- 6 -sulfanyl, formyl, carbamoyl, carbamate, C-i-Cs-alkyl, tri(Ci-C8-alkyl)silyl, C3- C7-cycloalkyl, C-i-Cs-halogenoalkyl having 1 to 5 halogen atoms, C3-C7-halogenocycloalkyl having 1 to 5 halogen atoms, C2-Cs-alkenyl, C2-Cs-alkynyl, Ci-Cs-alkylamino, di-C-i-Cs-alkylamino, C-i-Cs-alkoxy, C-i-Cs- halogenoalkoxy having 1 to 5 halogen atoms, C-i-C
  • heterocyclyl such as used in the expression “unsubstituted or substituted heterocyclyl” means, an unsaturated, saturated or partially saturated 5- to 7-membered ring, preferably a 5- to 6-membered ring, comprising from 1 to 4 heteroatoms independently selected in the list consisting of N, O and S.
  • heterocyclyl as used herein encompasses heteroaryl.
  • the expression“partially saturated or unsaturated fused bicyclic 9-, 10- or 1 1-membered heterocyclyl ring” designates fused bicyclic ring systems comprising a saturated ring fused with an unsaturated ring or two fused unsaturated rings, the bicyclic ring system being constituted from 9 to 1 1 skeletal atoms.
  • an alkyl group, an alkenyl group and an alkynyl group as well as moieties containing these terms can be linear or branched.
  • the term“carbocycle” designates a hydrocarbon ring.
  • the two substituents together with the nitrogen atom to which they are linked can form a heterocyclyl group, preferably a 5- to 7-membered heterocyclyl group, that can be substituted or that can include other hetero atoms, for example a morpholino group or piperidinyl group.
  • any of the compounds of the present invention can exist in one or more optical or chiral isomer forms depending on the number of asymmetric centres in the compound.
  • the invention thus relates equally to all optical isomers and racemic or scalemic mixtures thereof (the term "scalemic” denotes a mixture of enantiomers in different proportions) and to mixtures of all possible stereoisomers, in all proportions.
  • the diastereoisomers and/or the optical isomers can be separated according to methods which are known per se by the man ordinary skilled in the art.
  • any of the compounds of the present invention can also exist in one or more geometric isomer forms depending on the number of double bonds in the compound.
  • the invention thus relates equally to all geometric isomers and to all possible mixtures, in all proportions.
  • the geometric isomers can be separated according to general methods, which are known per se by the man ordinary skilled in the art.
  • any of the compounds of the present invention can also exist in one or more geometric isomer forms depending on the relative position (syn/anti or cis/trans) of the substituents of the chain or ring.
  • the invention thus relates equally to all syn/anti (or cis/trans) isomers and to all possible syn/anti (or cis/trans) mixtures, in all proportions.
  • the syn/anti (or cis/trans) isomers can be separated according to general methods, which are known per se by the man ordinary skilled in the art.
  • a compound of the invention can be present in tautomeric form, such a compound is understood herein above and herein below also to include, where applicable, corresponding tautomeric forms, even when these are not specifically mentioned in each case.
  • Z is preferably selected from the group consisting of hydrogen atom, halogen atom, unsubstituted or substituted Ci-C6-alkyl, Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted Ci-C6-alkoxy, Ci-C6-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different and cyano, more preferably Z is a hydrogen atom, an unsubstituted or substituted Ci-C6-alkyl (e.g. a methyl group) or a Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, even more preferably Z is a hydrogen atom.
  • X is preferably independently selected from the group consisting of halogen atom, unsubstituted or substituted Ci-C6-alkyl, Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted C2-Cs-alkenyl, unsubstituted or substituted C2-C8- alkynyl, unsubstituted or substituted C3-C7-cycloalkyl, hydroxyl, unsubstituted or substituted Ci-C6-alkoxy, Ci-C6-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted aryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C1-C6- alkylcarbonyl, unsubstituted or substituted Ci-C6-trialkylsily
  • Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different (e.g. a trifluoromethyl group), an unsubstituted or substituted Ci-C6-alkoxy (e.g. a methoxy group), an unsubstituted or substituted Ci-C6-halogenoalkoxy (e.g. a trifluoromethoxy group) or a trimethylsilyl group, even more preferably X is a halogen atom (e.g. a chlorine atom, a bromine atom or a fluorine atom), an unsubstituted Ci-C6-alkyl (e.g. a methyl group) or an unsubstituted Ci-C6-alkoxy (e.g. a methoxy group).
  • X is a halogen atom (e.g. a chlorine atom, a bromine atom or a fluorine atom), an unsub
  • n is preferably 0, 1 , 2, more preferably 0 or 1.
  • W is preferably CY 1 or N wherein Y 1 is preferably selected from the group consisting of hydrogen atom, halogen atom, unsubstituted or substituted Ci-C6-alkyl, Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted C3-C7-cycloalkyl, hydroxyl, unsubstituted or substituted Ci-C6-alkoxy, Ci-C6-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted Ci-C6-alkoxycarbonyl, formyl and cyano, more preferably Y 1 is hydrogen atom.
  • W is preferably CY 1 wherein Y 1 is selected from the group consisting of hydrogen atom, halogen atom, unsubstituted or substituted Ci-C6-alkyl, Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted C3-C7-cycloalkyl, hydroxyl, unsubstituted or substituted Ci-C6-alkoxy, Ci-C6-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted Ci-C6-alkoxycarbonyl, formyl and cyano, more preferably Y 1 is hydrogen atom.
  • Y 2 , Y 3 , Y 4 or Y 5 is preferably independently selected from the group consisting of hydrogen atom, halogen atom, unsubstituted or substituted Ci-C6-alkyl, Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted C3-C7-cycloalkyl, hydroxyl, unsubstituted or substituted Ci-C6-alkoxy, Ci-C6-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted Ci-C6-alkoxycarbonyl, formyl and cyano, more preferably Y 2 , Y 3 , Y 4 or Y 5 is independently a hydrogen atom, a halogen atom, an unsubstituted or substituted Ci-C6-alkyl, a Ci-C
  • Y 2 , Y 3 , Y 4 or Y 5 is independently a hydrogen atom or a halogen atom.
  • Y 2 , Y 3 and Y 4 are hydrogen atoms and Y 5 is a hydrogen atom or a halogen atom.
  • R 1a and R 1 b , or R 2a and R 2b together with the carbon atom to which they are linked may form a 3-, 4-, 5- or 6-membered, saturated or partially saturated, optionally substituted, carbocycle or heterocycle comprising at least 1 heteroatom selected in the list consisting of N,0 and S.
  • Examples of 3-, 4-, 5- or 6-membered, saturated or partially saturated, optionally substituted, carbocycle include cyclopropyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclopentenyl and cyclohexenyl.
  • Examples of 3-, 4-, 5- or 6-membered, saturated or partially saturated, optionally substituted, heterocycle include oxiranyl, aziridinyl, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, dihydrofuryl, dihydrothienyl, pyrrolidinyl, piperidinyl, dioxanyl, tetrahydropyranyl, hexahydropyridazinyl, hexahydropyrimidinyl and piperazinyl.
  • examples of these include indane and decalin.
  • R 1a and R 1 b , or R 2a and R 2b , together with the carbon atom to which they are linked may form an unsubstituted or substituted, saturated or partially unsaturated, spiro[n 1 ,n 2 ]-C5-Cn-alkyl comprising from 1 to 4 heteroatoms independently selected in the list consisting of N, O and S, wherein n 1
  • n 1 + n 2 4 to 10.
  • examples of these include spiro-[2,2]pentane and spiro-[2,3]hexane.
  • R 1a and R 1 b , or R 2a and R 2b , together with the carbon atom to which they are linked may form an unsubstituted or substituted, saturated or partially unsaturated, heterospiro[n 1 ,n 2 ]-C5-Cn-alkyl comprising from 1 to 4 heteroatoms independently selected in the list consisting of N, O and S, wherein n 1
  • n 1 + n 2 4 to 10.
  • An example of these includes 2-oxaspiro[3,3]heptane.
  • R 1a and R 1 b are preferably independently selected from the group consisting of hydrogen atom, halogen atom, unsubstituted or substituted Ci-C6-alkyl, unsubstituted or substituted C2-C6- alkenyl, unsubstituted or substituted C2-C6-halogenoalkenyl, unsubstituted or substituted C2-C6-alkynyl, unsubstituted or substituted C3-C7-cycloalkyl, unsubstituted or substituted C3-C7-cycloalkyl-Ci-C6-alkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocyclyl-Ci-C6-alkyl, unsubstituted or substituted heterocyclyl, and unsubstituted or substituted aryl-C-i-Cs-alkyl, or
  • R 1a and R 1 b together with the carbon atom to which they are linked may preferably
  • R 1a and R 1 b are each independently a hydrogen atom, an unsubstituted or substituted Ci-C6-alkyl (e.g. methyl group), or R 1a and R 1 b together form a 3-, 4-, 5- or 6- membered, saturated or partially saturated, optionally substituted, carbocycle (e.g.
  • spiro[n 1 ,n 2 ]-C5-Cn-alkyl wherein n 1 > 2 and n 1 + n 2 4 to 10 (e.g. spiro-[2,2]pentane).
  • L 1 is preferably CR 1a R 1 b wherein R 1a and R 1 b are independently a hydrogen atom or an unsubstituted C-i-Cs-alkyl.
  • R 2a and R 2b are preferably independently a hydrogen atom, a halogen atom, a hydroxyl, an unsubstituted or substituted Ci-C6-alkoxy, an unsubstituted or substituted Ci-C6-alkyl, an unsubstituted or substituted aryl, a hydroxyl, an unsubstituted or substituted C2-Cs-alkenyloxy, an unsubstituted or substituted C3-Cs-alkynyloxy, an unsubstituted or substituted aryl-Ci-C6-alkoxy, an unsubstituted or substituted heterocyclyl-Ci-C6-alkoxy or an unsubstituted or substituted partially saturated or unsaturated fused bicyclic 9-, 10- or 1 1-membered heterocyclyl-Ci-C6-alkoxy comprising from 1 to 5 heteroatoms independently selected in the list consisting of N, O and S.
  • unsubstituted or substituted aryl-Ci-C6-alkoxy examples include unsubstituted or substituted phenyl-Ci- C6-alkoxy wherein the phenyl group may be substituted by one or more group selected from the group consisting of unsubstituted or substituted Ci-C6-alkyl, Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, cyano, halogen, unsubstituted or substituted Ci-C6-alkylsulfonyl, unsubstituted or substituted Ci-C6-alkylsulfanyl unsubstituted or substituted aryl (e.g.
  • Ci-C6-alkoxy comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted aryloxy and unsubstituted or substituted aryl- Ci-C6-alkoxy, preferably unsubstituted Ci-C6-alkyl, C1-C6- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different,, halogen, unsubstituted Ci-C6-alkoxy and Ci-C6-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different.
  • unsubstituted or substituted heterocyclyl-Ci-C6-alkoxy examples include unsubstituted or substituted thiazolyl-Ci-C6-alkoxy and unsubstituted or substituted furanyl-Ci-C6-alkoxy.
  • Examples of unsubstituted or substituted partially saturated or unsaturated fused bicyclic 9-, 10- or 1 1- membered heterocyclyl-Ci-C6-alkoxy comprising from 1 to 5 heteroatoms independently selected in the list consisting of N, O and S include unsubstituted or substituted indazolyl--Ci-C6-alkoxy and unsubstituted or su bstituted benzoxazolyl-Ci -C6-al koxy.
  • R 2a and R 2b are more preferably independently a hydrogen atom, a halogen atom (e.g. fluorine atom), a hydroxyl, an unsubstituted or substituted Ci-C6-alkyl (e.g. a methyl group), an unsubstituted or substituted aryl (e.g. unsubstituted or substituted phenyl), an unsubstituted or substituted Ci-C6-alkoxy (e.g. a methoxy group), an unsubstituted or substituted aryloxy, an unsubstituted or substituted aryl-Ci-C6-alkoxy (e.g.
  • unsubstituted or substituted benzyloxy an unsubstituted or substituted C2-C8-alkenyloxy (e.g. allyloxy), an unsubstituted or substituted C3-Cs-alkynyloxy (e.g. propynyloxy), an unsubstituted or substituted aryl-Ci-C6-alkoxy (e.g.
  • the active ingredients are compounds of formula (I) wherein:
  • Y 1 is selected from the group consisting of hydrogen atom, halogen atom, unsubstituted or substituted Ci-C6-alkyl, Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted C3-C7-cycloalkyl, hydroxyl, unsubstituted or substituted Ci-C6-alkoxy, Ci-C6-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted Ci-C6-alkoxycarbonyl, formyl and cyano;
  • Y 2 , Y 3 , Y 4 or Y 5 is independently selected from the group consisting of hydrogen atom, halogen atom, unsubstituted or substituted Ci-C6-alkyl, Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted C3-C7-cycloalkyl, hydroxyl, unsubstituted or substituted Ci-C6-alkoxy, Ci-C6-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted Ci-C6-alkoxycarbonyl, formyl and cyano;
  • Z is selected from the group consisting of hydrogen atom, halogen atom, unsubstituted or substituted Ci-C6-alkyl, Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted Ci-C6-alkoxy, Ci-C6-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different and cyano;
  • A may be selected from the group consisting of pyrrolyl, furanyl, thienyl, thiazolyl, isothiazolyl, oxazolyl, imidazolyl, isoxazolyl, pyrazolyl, triazolyl, thiadiazolyl, oxadiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazynyl and triazinyl.
  • A is a 5- or 6-membered unsaturated heterocyclyl ring comprising 1 or 2 heteroatoms independently selected in the list consisting of N, O and S.
  • A is preferably selected from:
  • X and n are as herein-defined (being understood that n cannot exceed the number of available bonding sites), X a is selected from the group consisting consisting of C-i-Cs-alkyl, C-i-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, C 2 -Cs-alkenyl, C 2 -C8-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different, C 2 -Cs-alkynyl, C 2 -C8-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different, C3-C7-cycloalkyl, C3-C7- halogenocycloalkyl comprising up to 9 halogen atoms that can be the same or different, C3-C7-cycloalkyl- Ci-C8-alkyl, C 4 -C7-cycloal
  • n 0 or 1 and X is selected from the group consisting of hydrogen, halogen, unsubstituted Ci- Cs-alkyl and unsubstituted C-i-Cs-alkoxy.
  • compounds according to the present invention are compounds of formula (I)
  • A is selected from the group consisting of pyrrolyl, furanyl, thienyl, thiazolyl, isothiazolyl, oxazolyl, imidazolyl, isoxazolyl, pyrazolyl, triazolyl, thiadiazolyl, oxadiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazynyl and triazinyl;
  • Z is selected from the group consisting of hydrogen atom, halogen atom, unsubstituted or substituted Ci-C6-alkyl, Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted Ci-C6-alkoxy, Ci-C6-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different and cyano, preferably Z is a hydrogen atom, an unsubstituted or substituted Ci-C6-alkyl (e.g. a methyl group) or a Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, more preferably Z is a hydrogen atom;
  • n 0, 1 , 2, preferably 0 or 1 ;
  • X is independently selected from the group consisting of halogen atom, unsubstituted or substituted Ci-C6-alkyl, Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted C2-Cs-alkenyl, unsubstituted or substituted C2-Cs-alkynyl, unsubstituted or substituted C3-C7-cycloalkyl, hydroxyl, unsubstituted or substituted Ci-C6-alkoxy, Ci-C6-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted aryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted Ci-C6-alkylcarbonyl, unsubstituted or substituted Ci-C6-trialkylsilyl-Ci-C6-al
  • Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different (e.g. a trifluoromethyl group), an unsubstituted or substituted Ci-C6-alkoxy (e.g. a methoxy group), an unsubstituted or substituted Ci-C6-halogenoalkoxy (e.g. a trifluoromethoxy group) or a trimethylsilyl group, more preferably X is a halogen atom (e.g. a chlorine atom, a bromine atom or a fluorine atom), an unsubstituted Ci-C6-alkyl (e.g. a methyl group) or an unsubstituted Ci-C6-alkoxy (e.g. a methoxy group);
  • X is a halogen atom (e.g. a chlorine atom, a bromine atom or a fluorine atom), an unsubsti
  • W is CY 1 or N wherein Y 1 is selected from the group consisting of hydrogen atom, halogen atom, unsubstituted or substituted Ci-C6-alkyl, Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted C3-C7-cycloalkyl, hydroxyl, unsubstituted or substituted Ci-C6-alkoxy, Ci-C6-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted Ci-C6-alkoxycarbonyl, formyl and cyano, preferably Y 1 is hydrogen atom;
  • Y 2 , Y 3 , Y 4 and Y 5 are independently selected from the group consisting of hydrogen atom, halogen atom, unsubstituted or substituted Ci-C6-alkyl, Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted C3-C7-cycloalkyl, hydroxyl, unsubstituted or substituted Ci-C6-alkoxy, Ci-C6-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted Ci-C6-alkoxycarbonyl, formyl and cyano, preferably Y 2 , Y 3 , Y 4 and Y 5 are independently a hydrogen atom, a halogen atom, an unsubstituted or substituted Ci-C6-alkyl, a Ci-C6-halogenoalkyl compris
  • L 1 is CR 1a R 1b wherein R 1a and R 1b are independently a hydrogen atom or an unsubstituted C-i-Cs- alkyl;
  • compounds according to the present invention are compounds of formula (I)
  • thienyl preferably A IS selected from
  • Z is selected from the group consisting of hydrogen atom, unsubstituted or substituted Ci-C6-alkyl (e.g. a methyl group) and Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, preferably Z is a hydrogen atom;
  • n 0 or 1 ;
  • X is selected from the group consisting of halogen atom (e.g. a chlorine atom, a bromine atom or a fluorine atom), unsubstituted or substituted Ci-C6-alkyl (e.g. a methyl group), Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different (e.g. a trifluoromethyl group), unsubstituted or substituted Ci-C6-alkoxy (e.g. a methoxy group), unsubstituted or substituted Ci- C6-halogenoalkoxy (e.g.
  • halogen atom e.g. a chlorine atom, a bromine atom or a fluorine atom
  • Ci-C6-alkyl e.g. a methyl group
  • Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different (e.g.
  • X is a halogen atom (e.g. a chlorine atom, a bromine atom or a fluorine atom), an unsubstituted C1-C6- alkyl (e.g. a methyl group) or an unsubstituted Ci-C6-alkoxy (e.g. a methoxy group);
  • halogen atom e.g. a chlorine atom, a bromine atom or a fluorine atom
  • C1-C6- alkyl e.g. a methyl group
  • Ci-C6-alkoxy e.g. a methoxy group
  • W is CY 1 wherein Y 1 is selected from the group consisting of hydrogen atom, halogen atom, unsubstituted or substituted Ci-C6-alkyl, Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted C3-C7-cycloalkyl, hydroxyl, unsubstituted or substituted Ci-C6-alkoxy, Ci-C6-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted Ci-C6-alkoxycarbonyl, formyl and cyano, preferably Y 1 is hydrogen atom;
  • Y 2 , Y 3 , Y 4 and Y 5 are independently selected from the group consisting of hydrogen atom, halogen atom, unsubstituted or substituted Ci-C6-alkyl, Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different (e.g. trifluoromethyl) and cyano, preferably Y 2 , Y 3 , Y 4 or Y 5 are independently a hydrogen atom or a halogen atom, more preferably Y 2 , Y 3 and Y 4 are hydrogen atoms and Y 5 is a hydrogen atom or a halogen atom;
  • L 1 is CR 1a R 1 b wherein R 1a and R 1 b are independently a hydrogen atom or an unsubstituted C1-C6- alkyl;
  • compounds according to the present invention are compounds of formula (li) ( i.e . compounds of formula (I) wherein L 2 is CR 2a R 2b with R 2b is -OR 2c ):
  • A, n, X, Y 2 , Y 3 , Y 4 , Y 5 , W, Z, L 1 and R 2a are as herein-defined, and
  • R 2c is selected from the group consisting of unsubstituted or substituted Ci-C6-alkyl, Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted C2-C8- alkenyl, C2-C6-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted C3-Cs-alkynyl, C3-C8-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted C3-C7-cycloalkyl, C3-C7-halogenocycloalkyl comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted aryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C
  • unsubstituted or substituted aryl-Ci-C6-alkyl examples include benzyl and phenyl-Ci-C6-alkyl group wherein the phenyl group may be substituted by one or more group selected from the group consisting of unsubstituted or substituted Ci-C6-alkyl, Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different,, cyano, halogen, unsubstituted or substituted Ci-C6-alkylsulfonyl, unsubstituted or substituted Ci-C6-alkylsulfanyl, unsubstituted or substituted aryl (e.g.
  • Ci-C6-alkoxy comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted aryloxy and unsubstituted or substituted aryl- Ci-C6-alkoxy, preferably unsubstituted Ci-C6-alkyl, Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, halogen, unsubstituted Ci-C6-alkoxy and C1-C6- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different.
  • unsubstituted or substituted heterocyclyl-Ci-C6-alkyl examples include furanyl-Ci-C6-alkyl wherein the furanyl group may be substituted by one or more group selected from the group consisting of unsubstituted or substituted Ci-C6-alkyl, Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different,, cyano, halogen, unsubstituted or substituted Ci-C6-alkylsulfonyl, unsubstituted or substituted C1- C6-alkylsulfanyl, unsubstituted or substituted aryl (e.g.
  • Ci-C6-alkoxy comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted aryloxy and unsubstituted or substituted aryl- Ci-C6-alkoxy, preferably unsubstituted Ci-C6-alkyl, Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, halogen, unsubstituted Ci-C6-alkoxy and C1-C6- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different.
  • compounds according to the present invention are compounds of formula (li) (i.e. compounds of formula (I) wherein L 2 is CR 2a R 2b with R 2b is -OR 2c ):
  • thienyl preferably selected from
  • Z is selected from the group consisting of hydrogen atom, unsubstituted or substituted Ci-C6-alkyl (e.g. a methyl group) and Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, preferably Z is a hydrogen atom;
  • n 0 or 1 ;
  • X is selected from the group consisting of halogen atom (e.g. a chlorine atom, a bromine atom or a fluorine atom), unsubstituted or substituted Ci-C6-alkyl (e.g. a methyl group), Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different (e.g. a trifluoromethyl group), unsubstituted or substituted Ci-C6-alkoxy (e.g. a methoxy group), unsubstituted or substituted Ci- C6-halogenoalkoxy (e.g.
  • halogen atom e.g. a chlorine atom, a bromine atom or a fluorine atom
  • Ci-C6-alkyl e.g. a methyl group
  • Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different (e.g.
  • X is a halogen atom (e.g. a chlorine atom, a bromine atom or a fluorine atom), an unsubstituted C1-C6- alkyl (e.g. a methyl group) or an unsubstituted Ci-C6-alkoxy (e.g. a methoxy group);
  • halogen atom e.g. a chlorine atom, a bromine atom or a fluorine atom
  • C1-C6- alkyl e.g. a methyl group
  • Ci-C6-alkoxy e.g. a methoxy group
  • W is CY 1 wherein Y 1 is selected from the group consisting of hydrogen atom, halogen atom, unsubstituted or substituted Ci-C6-alkyl, Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted C3-C7-cycloalkyl, hydroxyl, unsubstituted or substituted Ci-C6-alkoxy, Ci-C6-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted Ci-C6-alkoxycarbonyl, formyl and cyano, preferably Y 1 is hydrogen atom; • Y 2 , Y 3 , Y 4 and Y 5 are independently selected from the group consisting of hydrogen atom, halogen atom, unsubstituted or substituted Ci-Ce-alkyl, Ci-C6-halogenoalkyl
  • Y 2 , Y 3 , Y 4 or Y 5 are independently a hydrogen atom or a halogen atom, more preferably Y 2 , Y 3 and Y 4 are hydrogen atoms and Y 5 is a hydrogen atom or a halogen atom;
  • L 1 is CR 1a R 1 b wherein R 1a and R 1 b are independently a hydrogen atom or a C-i-Cs-alkyl;
  • R 2a is a Ci-Ce-alkyl
  • R 2c is selected from the group consisting of R 2c is selected from the group consisting unsubstituted or substituted Ci-Ce-alkyl, Ci-C6-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted C2-Cs-alkenyl, C2-C6-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted C3-Cs-alkynyl, C3-C8-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted C3-C7-cycloalkyl, C3-C7-halogenocycloalkyl comprising up to 9 halogen atoms that can be the same or different, unsubstituted or substituted aryl, unsubstituted or substituted heterocyclyl,
  • R 2c include any of the R 2c groups disclosed in Table 1 c.
  • L 1 with one or more preferred features of A, L 2 , n, X, W, Y 2 Y 3 Y 4 , Y 5 and Z
  • L 2 with one or more preferred features of A, L 1 , n, X, W, Y 2 Y 3 Y 4 , Y 5 and Z
  • n with one or more preferred features of A, L 1 , L 2 , X, W, Y 2 Y 3 Y 4 , Y 5 and Z
  • Y 2 with one or more preferred features of A, L 1 , L 2 , n, X, W Y 3 Y 4 , Y 5 and Z
  • Y 3 with one or more preferred features of A, L 1 , L 2 , n, X, W Y 2 Y 4 , Y 5 and Z
  • Y 4 with one or more preferred features of A, L 1 , L 2 , n, X, W Y 2 Y 3 , Y 5 and Z
  • Y 5 with one or more preferred features of A, L 1 , L 2 , n, X, W Y 2 Y 3 , Y 4 and Z;
  • the said preferred features can also be selected among the more preferred features of each of A, L 1 , L 2 , n, X, W, Y 2 , Y 3 , Y 4 , Y 5 and Z so as to form most preferred subclasses of compounds according to the invention.
  • the present invention also relates to processes for the preparation of compounds of formula (I).
  • the compounds of formula (I) can be prepared by various routes in analogy to known processes (see e.g. and references therein). Non-limiting examples of suitable processes are herein described.
  • a compound of formula (I) may be directly obtained by performing processes P1 , P3, P5 or P8 or may be obtained by conversion or derivatization of another compound of formula (I) prepared in accordance with the processes described herein.
  • a compound of formula (I) can be converted into another compound of formula (I) by replacing one or more substituents of the starting compound of formula (I) by other substituents.
  • Non-limiting examples of such conversion or derivatization are described below (processes P6, PI, P1 1 , P12).
  • Compound of formula (I) or one of its salts as herein-defined can be prepared by a process P1 which comprises the step of reacting a compound of formula (II) or one of its salts with a compound of formula (III) as illustrated by the following reaction scheme:
  • U 1 is a fluorine atom, a bromine atom, a chlorine atom, an iodine atom, a mesyl group, a tosyl group, a triflyl group or a boron derivative such as a boronic acid, a boronic ester or a potassium trifluoroborate derivative.
  • Process P1 can be performed in the presence of a transition metal catalyst such as a metal salt or complex, and if appropriate in the presence of a ligand ; if appropriate in the presence of a base and if appropriate in the presence of a solvent.
  • Suitable metal derivatives for this purpose are transition metals such as palladium or copper.
  • Suitable palladium salts or complexes for this purpose are for example, palladium chloride, palladium acetate, tetrakis(triphenylphosphine)pailadium(0), bis(dibenzylideneacetone)pailadium(0), tris(dibenzylideneacetone)dipailadium(0), bis(triphenylphosphine)palladium(ll) dichloride, [1 , 1 - bis(diphenylphosphino)ferrocene]dichloropalladium(ll), bis(cinnamyl)dichlorodipalladium(ll), bis(allyl)- dichlorodipalladium(ll) or [1 , 1’-Bis(di-ferf-butylphosphino)ferrocene]dichloropalladium(ll).
  • a palladium complex in the reaction mixture by separate addition to the reaction of a palladium salt and a ligand or salt, such as triethylphosphine, tri-ferf-butylphosphine, tri -tert- butylphosphonium tetrafluoroborate, tricyclohexylphosphine, 2-(dicyclohexylphosphino)biphenyl, 2-(di-ferf- butylphosphino)biphenyl, 2-(dicyclohexylphosphino)-2'-(N,N-dimethylamino)biphenyl, 2-(tert- butylphosphino)-2'-(N,N-dimethylamino)biphenyl, 2-di-ferf-butylphosphino-2’,4’,6’-triisopropylbiphenyl 2- dicyclohexylphosphino-2’
  • catalyst and/or ligand from commercial catalogues such as“Metal Catalysts for Organic Synthesis” by Strem Chemicals or“Phosphorous Ligands and Compounds” by Strem Chemicals.
  • Suitable copper salts or complexes and their hydrates for this purpose are for example, copper metal, copper(l) iodide, copper(l) chloride, copper(l) bromide, copper(ll) chloride, copper(ll) bromide, copper(ll) oxide, copper(l) oxide, copper(ll) acetate, copper(l) acetate, copper(l) thiophene-2-carboxylate, copper(l) cyanide, copper(ll) sulfate, copper(ll) bis(2,2,6,6-tetramethyl-3,5-heptanedionate), copper(ll) trifluoromethanesulfonate, tetrakis(acetonitrile)copper(l) hexafluorophosphate, tetrakis(acetonitrile)- copper(l) tetrafluoroborate.
  • a copper complex in the reaction mixture by separate addition to the reaction of a copper salt and a ligand or salt, such as ethylenediamine, N,N-dimethylethylenediamine, N,N’- dimethylethylenediamine, rac- trans-1 ,2-diaminocyclohexane, rac-trans-N,N’-dimethylcyclohexane-1 ,2- diamine, 1 , 1’-binaphthyl-2, 2’-diamine, N,N,N’,N’-tetramethylethylenediamine, proline, N,N-dimethylglycine, quinolin-8-ol, pyridine, 2-aminopyridine, 4-(dimethylamino)pyridine, 2,2’-bipyridyl, 2,6-di(2-pyridyl)pyridine, 2-picolinic acid, 2-(dimethylaminomethyl)-3-hydroxypyridine, 1 ,10-phenan
  • Suitable bases for carrying out process P1 can be inorganic and organic bases which are customary for such reactions.
  • Suitable solvents for carrying out process P1 can be customary inert organic solvents. Preference is given to using, optionally halogenated, aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin ; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, 1 ,2-dichloroethane or trichloroethane ; ethers, such as diethyl ether, diisopropyl ether, methyl tert- butyl ether, methyl ferf-amyl ether, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, 1 ,2-dimethoxyethane, 1 ,2-dieth
  • Process P1 may be performed in an inert atmosphere such as argon or nitrogen atmosphere.
  • an inert atmosphere such as argon or nitrogen atmosphere.
  • 1 mole or an excess of compound of formula (III) and from 1 to 5 moles of base can be employed per mole of compound of formula (II).
  • palladium salts or complexes are used, from
  • O.01 to 20 mole percent of a palladium complex can be employed per mole of compound of formula (II).
  • copper salts or complexes are used, from 0.01 to 200 mole percent of a copper complex can be employed per mole of compound of formula (II). It is also possible to employ the reaction components in other ratios. Work-up is carried out by known methods.
  • a derivative of formula (III) or one of its salts can be prepared by a process P2 which comprises the deprotection of a derivative of formula (IV) as illustrated by the following reaction scheme:
  • A, n, X, L 1 and L 2 are as herein-defined and V represents a benzyl group, a 4-methoxybenzyl group, an allyl group, an unsubstituted or substituted Ci-C6-alkylsulfonyl such as a trifluoromethylsulfonyl, an unsubstituted or substituted phenylsulfonyl, such as a tolylsulfonyl, an unsubstituted or substituted Ci- C6-alkoxycarbonyl, such as a ferf-butoxycarbonyl, an unsubstituted or substituted benzyloxycarbonyl, an allyloxycarbonyl or a 2-trimethylsilylethyoxymethyl group.
  • Process P2 can be carried out according to known processes for removing protecting groups (Greene’s Protective Groups in Organic Synthesis; Peter G. M. Wuts; Wiley; Fifth Edition; 2014; 895-1 194).
  • protecting groups Greene’s Protective Groups in Organic Synthesis; Peter G. M. Wuts; Wiley; Fifth Edition; 2014; 895-1 194.
  • ferf-butoxycarbonyl protecting groups can be removed in an acidic medium (for example with hydrochloric acid or trifluoroacetic acid).
  • Benzylic and benzyloxycarbonyl protecting groups can be removed hydrogenolytically with hydrogen in the presence of a catalyst (for example palladium on activated carbon).
  • Compound of formula (I) or one of its salts as herein-defined can be prepared by a process P3 from a compound of formula (V) or one of its salts by an intermolecular cyclisation reaction as illustrated by the following reaction scheme:
  • A, n, X, Y 2 , Y 3 , Y 4 , Y 5 , W, Z, L 1 and L 2 are as herein-defined and U 2 is a chlorine atom or a fluorine atom.
  • process P3 can be performed in the presence of a base and if appropriate in the presence of a solvent, preferably under anhydrous conditions.
  • Suitable solvents for carrying out process P3 are not particularly limited. They can be customary inert organic solvents as long as it is not dissolving the compound to react therewith or exhibit any particular interaction therewith.
  • halogenated, aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, decalin, ISOPARTM E or ISOPARTM G, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, 1 ,2-dichloroethane or trichloroethane ; ethers, such as diethyl ether, diisopropyl ether, methyl tert- butyl ether, methyl ferf-amyl ether, dioxane, tetrahydrofuran, 2- methyltetrahydrofuran, 1 ,2-dimethoxyethane, 1 ,2-diethoxyethane or anisole ; nit
  • Suitable bases for carrying out process P3 can be inorganic and organic bases which are customary for such reactions such as the bases disclosed in connection with process P1.
  • Other suitable bases for carrying out process P3 according to the invention can be amides or organometallic derivatives. Preference is given to alkali metal amides, such as sodium amide or potassium amide ; organic amides, such as lithium diisopropylamine (LDA), lithium tetramethylpiperidide, lithium hexamethyldisilazane (LiHMDS), potassium hexamethyldisilazane (KHMDS) or sodium hexamethyldisilazane (NaHMDS) ; organolithium derivatives, such as methyl lithium, phenyllithium, n-butyllithium, sec-butyllithium, /so-butyllithium or ferf-butyllithium.
  • LDA lithium diisopropylamine
  • LiHMDS lithium tetramethylpipe
  • U 2 is a chlorine atom or a fluorine atom
  • k is 0, 1 or 2.
  • U 3 is a hydrogen atom, a hydroxyl group, a chlorine atom, an unsubstituted or substituted Ci-C6-alkylcarbonyl or an unsubstituted or substituted Ci-C6-alkylsulfanyl
  • Process P4 can be carried out according to known processes (The Chemistry of Functional Groups - The Chemistry of sulphonic acids, esters and their derivatives; Saul Patai, Avi Rappoport; Wiley-lnterscience; 1991 ; 351-399).
  • compounds of formula (V) can be directly cyclized to yield compounds of formula (I) according to process P3.
  • Compounds of formula (VI) can be prepared according to known processes (The Chemistry of Functional Groups - The Chemistry of sulphonic acids, esters and their derivatives; Saul Patai, Avi Rappoport; Wiley- lnterscience; 1991 ; 351-399; The Chemistry of Functional Groups - The Chemistry of sulphenic acids, esters and their derivatives; Saul Patai; Wiley-lnterscience; 1990; 187-292; The Chemistry of Functional Groups - The Chemistry of the thiol group, Part 1 ; Saul Patai; Wiley-lnterscience; 1974; 163-270; The Chemistry of Functional Groups - The Chemistry of sulphinic acids, esters and their derivatives; Saul Patai; Wiley-lnterscience; 1990; 185-216 and 577-602).
  • Compound of formula (I) or one of its salts as herein-defined can be prepared by a process P5 from a compound of formula (VII) or one of its salts by intramolecular cyclisation reaction:
  • A, n, X, Y 2 , Y 3 , Y 4 , Y 5 , W, Z, L 1 and L 2 are as herein-defined and U 4 is a bromine atom, a chlorine atom, an iodine atom, a mesyl group, a tosyl group, a triflyl group or a fluorine atom.
  • Process P5 can be performed in the presence of a transition metal catalyst such as palladium and if appropriate in the presence of a phosphine ligand or a N-heterocyclic carbene ligand; or copper and if appropriate in the presence of a ligand ; and if appropriate in the presence of a base and if appropriate in the presence of a solvent.
  • a transition metal catalyst such as palladium and if appropriate in the presence of a phosphine ligand or a N-heterocyclic carbene ligand; or copper and if appropriate in the presence of a ligand ; and if appropriate in the presence of a base and if appropriate in the presence of a solvent.
  • process P5 can be carried out in the presence of a catalyst, such as a metal salt or complex.
  • a catalyst such as a metal salt or complex.
  • Suitable metal derivatives for this purpose are transition metals such as palladium or copper.
  • process P5 can be carried out in the sole presence of a base.
  • Suitable metal salt or complex can be as disclosed in connection with process P1.
  • Suitable bases for carrying out process P5 can be inorganic and organic bases which are customary for such reactions, such as for instance the bases disclosed in connection with process P1.
  • Suitable solvents for carrying out process P5 can be customary inert organic solvents, such as for instance the solvents disclosed in connection with process P1.
  • Process P5 may be performed in an inert atmosphere such as argon or nitrogen atmosphere.
  • an inert atmosphere such as argon or nitrogen atmosphere.
  • process P5 from 1 to 5 moles of base can be employed per mole of compound of formula (VII).
  • palladium salts or complexes from 0.01 to 20 mole percent of a palladium complex can be employed per mole of compound of formula (VII).
  • copper salts or complexes from 0.01 to 200 mole percent of a copper complex can be employed per mole of compound of formula (VII). It is also possible to employ the reaction components in other ratios. Work-up is carried out by known methods.
  • Compounds of formula (VII) can be prepared according to known processes (The Chemistry of Functional Groups - The Chemistry of sulphonic acids, esters and their derivatives; Saul Patai, Avi Rappoport; Wiley- Interscience; 1991 ; 351-399).
  • Compound of formula (lb) or one of its salts as herein-defined (/.e. formula (!) wherein R 1b is not hydrogen) can be prepared by a process P6 which comprises the step of reacting a compound of formula (la) or one of its salts (/ ' .e. formula (!) wherein R 1b is hydrogen) with a compound of formula (VIII) as illustrated by the following reaction scheme :
  • R 1a and R 1 b are as herein-defined provided that R 1 b is not a hydrogen atom, and U 5 is a bromine atom, a chlorine atom, an iodine atom, a mesyl group or a tosyl group.
  • process P6 can be performed in the presence of a base and if appropriate in the presence of a solvent.
  • Suitable solvents for carrying out process P6 are not particularly limited. They can be customary inert organic solvents as long as it is not dissolving the compound to react therewith or exhibit any particular interaction therewith. Suitable solvents can be for instance the solvents disclosed in connection with process P3.
  • Suitable bases for carrying out process P6 can be inorganic and organic bases which are customary for such reactions, such as for instance the bases disclosed in connection with processes P1 and P3.
  • Compound of formula (Id) or one of its salts as herein-defined (/.e. formula (!) wherein L 1 is CH2 and R 1a is R 1a and R 2a is R 2a ) can be prepared by a process P7 which comprises the step of reacting a compound of formula (lc) or one of its salts with a compound of formula (IX) as illustrated by the following reaction scheme :
  • A, n, X, Y 2 , Y 3 , Y 4 , Y 5 , W, Z, R 1a and R 1 b are as herein-defined and U 6 is a leaving group such as an unsubstituted or substituted Ci-C6-alkoxy, an unsubstituted or substituted di-C-i-Cs-alkylamino or an unsubstituted or substituted N-[Ci-C6-alkoxy]-Ci-C6-alkylamino.
  • process P8 can be performed in the presence of a base and if appropriate in the presence of a solvent, preferably under anhydrous conditions.
  • Suitable solvents for carrying out process P8 are not particularly limited. They can be customary inert organic solvents as long as it is not dissolving the compound to react therewith or exhibit any particular interaction therewith, such as for instance the solvents disclosed in connection with process P3.
  • Suitable bases for carrying out process P8 can be inorganic and organic bases which are customary for such reactions, such as for instance the bases disclosed in connection with processes P1 and P3.
  • Compound of formula (X) or one of its salts as herein-defined can be prepared by a process P9 which comprises the step of reacting a compound of formula (XI) or one of its salts:
  • A, n, X, Y 2 , Y 3 , Y 4 , Y 5 , W and Z are as herein-defined, and U 6 represents a leaving group such as an unsubstituted or substituted Ci-C6-alkoxy, an unsubstituted or substituted di-C-i-Cs-alkylamino or an unsubstituted or substituted N-[Ci-C6-alkoxy]-Ci-C6-alkylannino; with a derivative of formula (Xla) or a derivative of formula (Xlb):
  • R 1a and R 1 b are as herein-defined and U 7 is a fluorine atom or a chlorine atom.
  • process P9 can be performed in the presence of a base and if appropriate in the presence of a solvent, preferably under anhydrous conditions.
  • Suitable solvents for carrying out process P9 are not particularly limited. They can be customary inert organic solvents as long as it is not dissolving the compound to react therewith or exhibit any particular interaction therewith, such as for instance the solvents disclosed in connection with process P3.
  • Suitable bases for carrying out process P9 can be inorganic and organic bases which are customary for such reactions, such as for instance the bases disclosed in connection with processes P1 and P3.
  • U 1 is a fluorine atom, a bromine atom, a chlorine atom, an iodine atom, a mesyl group, a tosyl group or a triflyl group and U 6 represents a leaving group such as an unsubstituted or substituted Ci-C6-alkoxy, an unsubstituted or substituted di-C-i-Cs- alkylamino or an unsubstituted or substituted N-[Ci-C6-alkoxy]-Ci-C6-alkylamino.
  • Process P10a can be carried out with similar reactions conditions than the ones disclosed in process P1.
  • Compound of formula (XI) or one of its salts as herein-defined can be prepared by a process P10b which comprises the step of reacting a compound of formula (XIV) or one of its salts with a compound of formula (XV) as illustrated by the following reaction scheme :
  • U 1 is a fluorine atom, a bromine atom, a chlorine atom, an iodine atom, a mesyl group, a tosyl group or a triflyl group and U 6 represents a leaving group such as an unsubstituted or substituted Ci-C6-alkoxy, an unsubstituted or substituted di-C-i-Cs- alkylamino or an unsubstituted or substituted N-[Ci-C6-alkoxy]-Ci-C6-alkylamino.
  • Process P10b can be carried out with similar reactions conditions than the ones disclosed in process P1.
  • A, n, X, Y 2 , Y 3 , Y 4 , Y 5 , W, Z, R 1a and R 1 b are as herein-defined.
  • Process P1 1 can be performed in the presence of a fluorinating agent and if appropriate in the presence of a solvent.
  • Suitable fluorinating agents for carrying out process P1 1 are not particularly limited provided they are used for fluorination.
  • fluorinating agents include sulfur fluorides such as sulfur tetrafluoride, diethylaminosulfur trifluoride, morpholinosulfur trifluoride, bis(2-methoxyethyl)aminosulfur trifluoride, 2,2- difluoro-1 ,3-dimethylimidazolidine or 4-ferf-butyl-2,6-dimethylphenylsulfur trifluoride.
  • Suitable solvents for carrying out process P1 1 are not particularly limited.
  • Suitable solvents can be for instance the solvents disclosed in connection with process P3.
  • process P1 1 1 to 20 moles of fluorinating agent can be employed per mole of compound of formula (le). It is also possible to employ the reaction components in other ratios. Work-up is carried out by known methods.
  • A, n, X, Y 2 , Y 3 , Y 4 , Y 5 , W, Z, R 2a and L 1 are as herein-defined.
  • Process P12 can be carried out with similar reactions conditions than the ones disclosed in process P11.
  • Compounds of formula (Ig) or one of its salts can be prepared from a compound of formula (le) or one of its salts with classical functional group interconversion methods known by the person skilled in the art such as reductions or additions of an organometallic reagent.
  • R 2c is C-i-Cs-alkyl, C-i-Cs- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, C2-Cs-alkenyl, C2-C8- halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different, C3-Cs-alkynyl, C3-C8- halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different, C3-C7-cycloalkyl, C3- C7-halogenocycloalkyl comprising up to 9 halogen atoms that can be the same or different, C3-C7- cycloalkyl-Ci-C8-alkyl, aryl
  • N-oxides of compounds of formula (I) can be prepared by classical oxidation methods known by the person skilled in the art. Processes P1 , P2, P3, P4, P5, P6, P7, P8, P9, P10 P1 1 and P12 are generally carried out under atmospheric pressure. It is also possible to operate under elevated or reduced pressure.
  • reaction temperatures can be varied within a relatively wide range. In general, these processes are carried out at temperatures from - 78 °C to 200 °C, preferably from - 78 °C to 150 °C.
  • a way to control the temperature for the processes is to use microwave technology.
  • reaction mixture is treated with water and the organic phase is separated off and, after drying, concentrated under reduced pressure. If appropriate, the remaining residue can, be freed by customary methods, such as chromatography, crystallization or distillation, from any impurities that may still be present.
  • the compounds of formula (I) can be prepared according to the general processes of preparation described above and by classical functional group interconversion methods known by the person skilled in the art. It will nevertheless be understood that, on the basis of his general knowledge and of available publications, the skilled worker will be able to adapt the methods according to the specifics of each compound, which it is desired to synthesize.
  • the present invention also relates to intermediates for the preparation of compounds of formula (I).
  • A, n and L 2 are as herein-defined ;
  • X b is independently selected from the group consisting of halogen atom, C-i-Cs-alkyl, C-i-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, C2-Cs-alkenyl, C2-Cs-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different, C2-Cs-alkynyl, C2-Cs-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different, C3-C7-cycloalkyl, C 4 -C7-cycloalkenyl, hydroxyl, C-i-Cs-alkoxy, C-i-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, formyl, C-i-Cs-alkylcarbonyl, (hydroxyimino)Ci-C8-alkyl, (
  • V is a benzyl group, a 4-methoxybenzyl group, an allyl group, an unsubstituted or substituted C1-C6- alkylsulfonyl, a trifluoromethylsulfonyl, an unsubstituted or substituted phenylsulfonyl, an unsubstituted or substituted Ci-C6-alkoxycarbonyl, an unsubstituted or substituted benzyloxycarbonyl, an allyloxycarbonyl or a 2-trimethylsilylethyoxynnethyl group ;
  • the present invention also relates to compounds of formula (V) and (VI) as well as their salts :
  • A, n, X, Y 2 , Y 3 , Y 4 , Y 5 , W, Z, L 1 and L 2 are as herein-defined ;
  • k 0, 1 or 2 ;
  • U 2 is a chlorine atom or a fluorine atom ;
  • the present invention also relates to compounds of formula (VII) as well as their salts :
  • A, n, X, Y 2 , Y 3 , Y 4 , Y 5 , W, Z, L 1 and L 2 are as herein-defined ;
  • U 4 is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a mesyl group, a tosyl group, a mesyl group or a triflyl group.
  • the present invention also relates to compounds of formula (X) as well as their salts :
  • A, n, X, Y 2 , Y 3 , Y 4 , Y 5 , W, Z, R 1a and R 1b are as herein-defined ;
  • U 6 is an unsubstituted or substituted Ci-C6-alkoxy, an unsubstituted or substituted di-C-i-Cs-alkylamino or an unsubstituted or substituted N-[Ci-C6-alkoxy]-Ci-C6-alkylamino.
  • the present invention also relates to compounds of formula (Xla) as well as their salts
  • X b is independently selected from the group consisting of halogen atom, C-i-Cs-alkyl, C-i-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, C2-Cs-alkenyl, C2-C8-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different, C2-Cs-alkynyl, C2-C8-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different, C3-C7-cycloalkyl, C 4 -C7-cycloalkenyl, hydroxyl, C-i-Cs-alkoxy, C-i-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, formyl
  • Z a is selected from the group consisting of hydrogen atom, C-i-Cs-alkyl, C-i-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, C2-Cs-alkenyl, C2-C8-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different, C2-Cs-alkynyl, C2-C8-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different, C3-C7-cycloalkyl, C 4 -C7-cycloalkenyl, aryl, heterocyclyl, formyl, C-i-Cs-alkylcarbonyl, (hydroxyimino)Ci-C8-alkyl, (Ci-C8-alkoxyimino)Ci-C8-alkyl, carboxyl, C-i-Cs-alkoxycarbonyl, carb
  • U 6 is an unsubstituted or substituted Ci-C6-alkoxy, an unsubstituted or substituted di-C-i-Cs-alkylamino or an unsubstituted or substituted N-[Ci-C6-alkoxy]-Ci-C6-alkylamino ;
  • compositions and formulations are provided.
  • the present invention further relates to a composition, in particular a composition for controlling unwanted microorganisms, comprising one or more compounds of formula (I).
  • the composition is preferably is a fungicidal composition.
  • the composition typically comprises one or more compounds of formula (I) and one or more acceptable carriers, in particular one or more agriculturally acceptable carriers.
  • a carrier is a solid or liquid, natural or synthetic, organic or inorganic substance that is generally inert.
  • the carrier generally improves the application of the compounds, for instance, to plants, plants parts or seeds.
  • suitable solid carriers include, but are not limited to, ammonium salts, natural rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth, and synthetic rock flours, such as finely divided silica, alumina and silicates.
  • typically useful solid carriers for preparing granules include, but are not limited to crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, synthetic granules of inorganic and organic flours and granules of organic material such as paper, sawdust, coconut shells, maize cobs and tobacco stalks.
  • suitable liquid carriers include, but are not limited to, water, organic solvents and combinations thereof.
  • suitable solvents include polar and nonpolar organic chemical liquids, for example from the classes of aromatic and nonaromatic hydrocarbons (such as cyclohexane, paraffins, alkylbenzenes, xylene, toluene alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride), alcohols and polyols (which may optionally also be substituted, etherified and/or esterified, such as butanol or glycol), ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone), esters (including fats and oils) and (poly)ethers, unsubstituted and substituted amines, amides (such as dimethylformamide), lactams (such as N-alkylpyrrolidones) and lactones, sulphone
  • the carrier may also be a liquefied gaseous extender, i.e. liquid which is gaseous at standard temperature and under standard pressure, for example aerosol propellants such as halohydrocarbons, butane, propane, nitrogen and carbon dioxide.
  • the amount of carrier typically ranges from 1 to 99.99%, preferably from 5 to 99.9%, more preferably from 10 to 99.5%, and most preferably from 20 to 99 % by weight of the composition.
  • composition may further comprise one or more acceptable auxiliaries which are customary for formulating compositions (e.g. agrochemical compositions), such as one or more surfactants.
  • acceptable auxiliaries which are customary for formulating compositions (e.g. agrochemical compositions), such as one or more surfactants.
  • the surfactant can be an ionic (cationic or anionic) or non-ionic surfactant, such as ionic or non-ionic emulsifier(s), foam former(s), dispersant(s), wetting agent(s) and any mixtures thereof.
  • surfactants include, but are not limited to, salts of polyacrylic acid, salts of lignosulphonic acid, salts of phenolsulphonic acid or naphthalenesulphonic acid, polycondensates of ethylene and/or propylene oxide with fatty alcohols, fatty acids or fatty amines (polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers), substituted phenols (preferably alkylphenols or arylphenols), salts of sulphosuccinic esters, taurine derivatives (preferably alkyl taurates), phosphoric esters of polyethoxylated alcohols or phenols, fatty esters of polyols and derivatives of compounds containing sulphates, sulphonates, phosphates (for example, alkylsulphonates, alkyl sulphates, arylsulphonates) and protein hydrolysates, lignosulphite
  • auxiliaries which are customary for formulating agrochemical compositions include water repellents, siccatives, binders (adhesive, tackifier, fixing agent, such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, natural phospholipids such as cephalins and lecithins and synthetic phospholipids, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose), thickeners, stabilizers (e.g.
  • dyes or pigments such as inorganic pigments, e.g. iron oxide, titanium oxide and Prussian Blue ; organic dyes, e.g. alizarin, azo and metal phthalocyanine dyes), antifoams (e.g. silicone antifoams and magnesium stearate), preservatives (e.g.
  • dichlorophene and benzyl alcohol hemiformal secondary thickeners (cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica), stickers, gibberellins and processing auxiliaries, mineral and vegetable oils, perfumes, waxes, nutrients (including trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc), protective colloids, thixotropic substances, penetrants, sequestering agents and complex formers.
  • secondary thickeners cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica
  • stickers gibberellins and processing auxiliaries
  • mineral and vegetable oils perfumes
  • waxes including trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc
  • protective colloids including trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molyb
  • auxiliaries are related to the intended mode of application of the compound of the formula (I) and/or on the physical properties. Furthermore, the auxiliaries may be chosen to impart particular properties (technical, physical and/or biological properties) to the compositions or use forms prepared therefrom. The choice of auxiliaries may allow customizing the compositions to specific needs.
  • composition of the invention may be in any customary form, such as solutions (e.g. aqueous solutions), emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, granules for broadcasting, suspoemulsion concentrates, natural or synthetic products impregnated with the compound of the invention, fertilizers and also microencapsulations in polymeric substances.
  • solutions e.g. aqueous solutions
  • emulsions e.g. aqueous solutions
  • emulsions e.g. aqueous solutions
  • emulsions e.g. aqueous solutions
  • emulsions e.g. aqueous solutions
  • emulsions e.g. aqueous solutions
  • emulsions e.g. aqueous solutions
  • emulsions e.g. aqueous solutions
  • emulsions
  • composition of the invention may be provided to the end user as ready-for-use formulation, i.e. the compositions may be directly applied to the plants or seeds by a suitable device, such as a spraying or dusting device.
  • a suitable device such as a spraying or dusting device.
  • the compositions may be provided to the end user in the form of concentrates, which have to be diluted, preferably with water, prior to use.
  • composition of the invention can be prepared in conventional manners, for example by mixing the compound of the invention with one or more suitable auxiliaries, such as disclosed herein above.
  • composition according to the invention contains generally from 0.01 to 99% by weight, from 0.05 to 98% by weight, preferably from 0.1 to 95% by weight, more preferably from 0.5 to 90% by weight, most preferably from 1 to 80 % by weight of the compound of the invention.
  • the compound and the composition of the invention can be mixed with other active ingredients like fungicides, bactericides, acaricides, nematicides, insecticides, herbicides, fertilizers, growth regulators, safeners or semiochemicals. This may allow to broaden the activity spectrum or to prevent development of resistance. Examples of known fungicides, insecticides, acaricides, nematicides and bactericides are disclosed in the Pesticide Manual, 17th Edition.
  • Inhibitors of the ergosterol biosynthesis for example (1.001 ) cyproconazole, (1.002) difenoconazole, (1.003) epoxiconazole, (1.004) fenhexamid, (1.005) fenpropidin, (1.006) fenpropimorph, (1.007) fenpyrazamine, (1.008) fluquinconazole, (1.009) flutriafol, (1.010) imazalil, (1.01 1 ) imazalil sulfate, (1 .012) ipconazole, (1.013) metconazole, (1.014) myclobutanil, (1.015) paclobutrazol, (1.016) prochloraz, (1.017) propiconazole, (1.018) prothioconazole, (1 .019) Pyrisoxazole, (1 .020) spiroxamine, (1.021 ) tebuconazole, (1.022) te
  • Inhibitors of the respiratory chain at complex I or II for example (2.001 ) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxin, (2.005) fluopyram, (2.006) flutolanil, (2.007) fluxapyroxad, (2.008) furametpyr, (2.009) Isofetamid, (2.010) isopyrazam (anti-epimeric enantiomer 1 R,4S,9S), (2.01 1 ) isopyrazam (anti-epimeric enantiomer 1 S,4R,9R), (2.012) isopyrazam (anti-epimeric racemate 1 RS,4SR,9SR), (2.013) isopyrazam (mixture of syn-epimeric racemate 1 RS,4SR,9RS and anti-epimeric racemate 1 RS,4SR,9SR), (2.014) isopyrazam (syn-epimeric enanti
  • Inhibitors of the respiratory chain at complex III for example (3.001 ) ametoctradin, (3.002) amisulbrom, (3.003) azoxystrobin, (3.004) coumethoxystrobin, (3.005) coumoxystrobin, (3.006) cyazofamid, (3.007) dimoxystrobin, (3.008) enoxastrobin, (3.009) famoxadone, (3.010) fenamidone, (3.01 1 ) flufenoxystrobin, (3.012) fluoxastrobin, (3.013) kresoxim-methyl, (3.014) metominostrobin, (3.015) orysastrobin, (3.016) picoxystrobin, (3.017) pyraclostrobin, (3.018) pyrametostrobin, (3.019) pyraoxystrobin, (3.020) trifloxystrobin, (3.021 ) (2E)-2- ⁇ 2-[( ⁇ [(1 E)-1-(2-(
  • Inhibitors of the mitosis and cell division for example (4.001 ) carbendazim, (4.002) diethofencarb, (4.003) ethaboxam, (4.004) fluopicolide, (4.005) pencycuron, (4.006) thiabendazole, (4.007) thiophanate- methyl, (4.008) zoxamide, (4.009) 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine, (4.010) 3- chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, (4.01 1 ) 3-chloro-5-(6-chloropyridin-3- yl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine, (4.012) 4-(2-bromo-4-fluorophenyl)-N-(2,6-difluoroph
  • Inhibitors of the amino acid and/or protein biosynthesis for example (7.001 ) cyprodinil, (7.002) kasugamycin, (7.003) kasugamycin hydrochloride hydrate, (7.004) oxytetracycline, (7.005) pyrimethanil, (7.006) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinoline.
  • Inhibitors of the ATP production for example (8.001 ) silthiofam.
  • Inhibitors of the cell wall synthesis for example (9.001 ) benthiavalicarb, (9.002) dimethomorph, (9.003) flumorph, (9.004) iprovalicarb, (9.005) mandipropamid, (9.006) pyrimorph, (9.007) valifenalate, (9.008) (2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one, (9.009) (2Z)-3-(4- tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one.
  • Inhibitors of the lipid and membrane synthesis for example (10.001 ) propamocarb, (10.002) propamocarb hydrochloride, (10.003) tolclofos-methyl.
  • Inhibitors of the melanin biosynthesis for example (1 1 .001 ) tricyclazole, (1 1.002) 2,2,2-trifluoroethyl ⁇ 3- methyl-1-[(4-methylbenzoyl)amino]butan-2-yl ⁇ carbamate.
  • Inhibitors of the nucleic acid synthesis for example (12.001 ) benalaxyl, (12.002) benalaxyl-M (kiralaxyl), (12.003) metalaxyl, (12.004) metalaxyl-M (mefenoxam).
  • Inhibitors of the signal transduction for example (13.001 ) fludioxonil, (13.002) iprodione, (13.003) procymidone, (13.004) proquinazid, (13.005) quinoxyfen, (13.006) vinclozolin.
  • the compound and the composition of the invention have potent microbicidal activity. They can be used for controlling unwanted microorganisms, such as unwanted fungi and bacteria. They can be particularly useful in crop protection (they control microorganisms that cause plants diseases) or for protecting materials (e.g. industrial materials, timber, storage goods) as described in more details herein below. More specifically, the compound and the composition of the invention can be used to protect seeds, germinating seeds, emerged seedlings, plants, plant parts, fruits, harvest goods and/or the soil in which the plants grow from unwanted microorganisms.
  • Control or controlling as used herein encompasses protective, curative and eradicative treatment of unwanted microorganisms.
  • Unwanted microorganisms may be pathogenic bacteria, pathogenic virus, pathogenic oomycetes or pathogenic fungi, more specifically phytopathogenic bacteria phytopathogenic virus, phytopathogenic oomycetes or phytopathogenic fungi. As detailed herein below, these phytopathogenic microorganims are the causal agents of a broad spectrum of plants diseases.
  • the compound and the composition of the invention can be used as fungicides.
  • fungicide refers to a compound or composition that can be used in crop protection for the control of unwanted fungi, such as Plasmodiophoromycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes and/or for the control of Oomycetes.
  • the present invention also relates to a method for controlling unwanted microorganisms, such as unwanted fungi, oomycetes and bacteria, comprising the step of applying at least one compound of the invention or at least one composition of the invention to the microorganisms and/or their habitat (to the plants, plant parts, seeds, fruits or to the soil in which the plants grow).
  • unwanted microorganisms such as unwanted fungi, oomycetes and bacteria
  • Suitable substrates that may be used for cultivating plants include inorganic based substrates, such as mineral wool, in particular stone wool, perlite, sand or gravel; organic substrates, such as peat, pine bark or sawdust; and petroleum based substrates such as polymeric foams or plastic beads.
  • Effective and plant-compatible amount means an amount that is sufficient to control or destroy the fungi present or liable to appear on the cropland and that does not entail any appreciable symptom of phytotoxicity for said crops. Such an amount can vary within a wide range depending on the fungus to be controlled, the type of crop, the crop growth stage, the climatic conditions and the respective compound or composition of the invention used. This amount can be determined by systematic field trials that are within the capabilities of a person skilled in the art.
  • the compound and the composition of the invention may be applied to any plants or plant parts.
  • Plants mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
  • Crop plants may be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the genetically modified plants (GMO or transgenic plants) and the plant cultivars which are protectable and non-protectable by plant breeders’ rights.
  • Plant parts are understood to mean all parts and organs of plants above and below the ground, such as shoot, leaf, flower and root, examples of which include leaves, needles, stalks, stems, flowers, fruit bodies, fruits and seeds, and also roots, tubers and rhizomes.
  • the plant parts also include harvested material and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, slips and seeds.
  • Plants which may be treated in accordance with the methods of the invention include the following: cotton, flax, grapevine, fruit, vegetables, such as Rosaceae sp.
  • pome fruits such as apples and pears, but also stone fruits such as apricots, cherries, almonds and peaches, and soft fruits such as strawberries
  • Ribesioidae sp. Juglandaceae sp.
  • Betulaceae sp. Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (for example banana trees and plantations), Rubiaceae sp.
  • Theaceae sp. for example coffee
  • Theaceae sp. Sterculiceae sp.
  • Rutaceae sp. for example lemons, oranges and grapefruit
  • Solanaceae sp. for example tomatoes
  • Liliaceae sp. for example lettuce
  • Umbelliferae sp. for example lettuce
  • Umbelliferae sp. for example lettuce
  • Umbelliferae sp. for example lettuce
  • Cicurbitaceae sp. for example cucumber
  • Alliaceae sp. for example leek, onion
  • Papilionaceae sp. for example peas
  • major crop plants such as Gramineae sp.
  • Asteraceae sp. for example sunflower
  • Brassicaceae sp. for example white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes, and oilseed rape, mustard, horseradish and cress
  • Fabacae sp. for example bean, peanuts
  • Papilionaceae sp. for example soya bean
  • Solanaceae sp. for example potatoes
  • Chenopodiaceae sp. for example sugar beet, fodder beet, swiss chard, beetroot
  • useful plants and ornamental plants for gardens and wooded areas and genetically modified varieties of each of these plants.
  • wild plant species and plant cultivars or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and also parts thereof, are treated in accordance with the methods of the invention.
  • transgenic plants and plant cultivars obtained by genetic engineering methods if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated in accordance with the methods of the invention. More preferably, plants of the plant cultivars which are commercially available or are in use are treated in accordance with the invention.
  • Plant cultivars are understood to mean plants which have new properties ("traits") and have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They can be cultivars, varieties, bio- or genotypes.
  • GMOs genetically modified organisms
  • Genetically modified plants are plants of which a heterologous gene has been stably integrated into genome.
  • the expression“heterologous gene” essentially means a gene which is provided or assembled outside the plant and when introduced in the nuclear, chloroplastic or mitochondrial genome gives the transformed plant new or improved agronomic or other properties by expressing a protein or polypeptide of interest or by downregulating or silencing other gene(s) which are present in the plant (using for example, antisense technology, cosuppression technology, RNA interference - RNAi - technology or microRNA - miRNA - technology).
  • a heterologous gene that is located in the genome is also called a transgene.
  • a transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.
  • Plants and plant cultivars which can be treated by the above disclosed methods include all plants which have genetic material which impart particularly advantageous, useful traits to these plants (whether obtained by breeding and/or biotechnological means).
  • Plants and plant cultivars which can be treated by the above disclosed methods include plants and plant cultivars which are resistant against one or more biotic stresses, i.e. said plants show a better defense against animal and microbial pests, such as against nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and/or viroids.
  • Plants and plant cultivars which can be treated by the above disclosed methods include those plants which are resistant to one or more abiotic stresses.
  • Abiotic stress conditions may include, for example, drought, cold temperature exposure, heat exposure, osmotic stress, flooding, increased soil salinity, increased mineral exposure, ozone exposure, high light exposure, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients, shade avoidance.
  • Plants and plant cultivars which can be treated by the above disclosed methods include those plants characterized by enhanced yield characteristics. Increased yield in said plants can be the result of, for example, improved plant physiology, growth and development, such as water use efficiency, water retention efficiency, improved nitrogen use, enhanced carbon assimilation, improved photosynthesis, increased germination efficiency and accelerated maturation. Yield can furthermore be affected by improved plant architecture (under stress and non-stress conditions), including but not limited to, early flowering, flowering control for hybrid seed production, seedling vigor, plant size, internode number and distance, root growth, seed size, fruit size, pod size, pod or ear number, seed number per pod or ear, seed mass, enhanced seed filling, reduced seed dispersal, reduced pod dehiscence and lodging resistance.
  • improved plant architecture under stress and non-stress conditions
  • Further yield traits include seed composition, such as carbohydrate content and composition for example cotton or starch, protein content, oil content and composition, nutritional value, reduction in anti-nutritional compounds, improved processability and better storage stability.
  • Plants and plant cultivars which can be treated by the above disclosed methods include plants and plant cultivars which are hybrid plants that already express the characteristic of heterosis or hybrid vigor which results in generally higher yield, vigor, health and resistance towards biotic and abiotic stresses.
  • Plants and plant cultivars obtained by plant biotechnology methods such as genetic engineering
  • plants and plant cultivars which can be treated by the above disclosed methods include plants and plant cultivars which are herbicide-tolerant plants, i.e. plants made tolerant to one or more given herbicides.
  • Plants and plant cultivars which can be treated by the above disclosed methods include plants and plant cultivars which are insect-resistant transgenic plants, i.e. plants made resistant to attack by certain target insects. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such insect resistance.
  • Plants and plant cultivars obtained by plant biotechnology methods such as genetic engineering
  • Plants and plant cultivars which can be treated by the above disclosed methods include plants and plant cultivars which are tolerant to abiotic stresses. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such stress resistance.
  • Plants and plant cultivars obtained by plant biotechnology methods such as genetic engineering which can be treated by the above disclosed methods include plants and plant cultivars which show altered quantity, quality and/or storage-stability of the harvested product and/or altered properties of specific ingredients of the harvested product.
  • Plants and plant cultivars obtained by plant biotechnology methods such as genetic engineering which can be treated by the above disclosed methods include plants and plant cultivars, such as cotton plants, with altered fiber characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered fiber characteristics.
  • Plants and plant cultivars which can be treated by the above disclosed methods include plants and plant cultivars, such as oilseed rape or related Brassica plants, with altered oil profile characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered oil profile characteristics. Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which can be treated by the above disclosed methods include plants and plant cultivars, such as oilseed rape or related Brassica plants, with altered seed shattering characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered seed shattering characteristics and include plants such as oilseed rape plants with delayed or reduced seed shattering. Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which can be treated by the above disclosed methods include plants and plant cultivars, such as Tobacco plants, with altered post-translational protein modification patterns.
  • phytopathogenic microorganisms such as phytopathogenic fungi, causing diseases, such as:
  • Blumeria species e.g. Blumeria graminis
  • Podosphaera species e.g. Podosphaera leucotricha
  • Sphaerotheca species e.g. Sphaerotheca fuliginea
  • Uncinula species e.g. Uncinula necator
  • Gymnosporangium species e.g. Gymnosporangium sabinae
  • Hemileia species e.g. Hemileia vastatrix
  • Phakopsora species e.g. Phakopsora pachyrhizi or Phakopsora meibomiae
  • Puccinia species e.g. Puccinia recondita, Puccinia graminis or Puccinia striiformis
  • Uromyces species e.g. Uromyces appendiculatus
  • Albugo species e.g. Albugo Candida
  • Bremia species e.g. Bremia lactucae
  • Peronospora species e.g. Peronospora pisi or P. brassicae
  • Phytophthora species e.g. Phytophthora infestans
  • Plasmopara species e.g. Plasmopara viticola
  • Pseudoperonospora species e.g. Pseudoperonospora humuli or Pseudoperonospora cubensis
  • Pythium species e.g. Pythium ultimum
  • Pythium species e.g. Pythium ultimum
  • leaf blotch diseases and leaf wilt diseases caused, for example, by Alternaria species (e.g. Alternaria solani), Cercospora species (e.g. Cercospora beticola), Cladiosporium species (e.g. Cladiosporium cucumerinum), Cochliobolus species (e.g. Cochliobolus sativus (conidial form: Drechslera, syn: Helminthosporium) or Cochliobolus miyabeanus), Colletotrichum species (e.g. Colletotrichum lindemuthanium), Cycloconium species (e.g. Cycloconium oleaginum), Diaporthe species (e.g.
  • Diaporthe citri Elsinoe species (e.g. Elsinoe fawcettii), Gloeosporium species (e.g. Gloeosporium laeticolor), Glomerella species (e.g. Glomerella cingulate), Guignardia species (e.g. Guignardia bidwelli), Leptosphaeria species (e.g. Leptosphaeria maculans), Magnaporthe species (e.g. Magnaporthe grisea), Microdochium species (e.g. Microdochium nivale), Mycosphaerella species (e.g.
  • Phaeosphaeria species e.g. Phaeosphaeria nodorum
  • Corticium species e.g. Corticium graminearum
  • Fusarium species e.g. Fusarium oxysporum
  • Gaeumannomyces species e.g. Gaeumannomyces graminis
  • Plasmodiophora species e.g. Plasmodiophora brassicae
  • Rhizoctonia species e.g. Rhizoctonia solani
  • Sarocladium species e.g. Sarocladium oryzae
  • Sclerotium species e.g. Sclerotium oryzae
  • Tapesia species e.g. Tapesia acuformis
  • Thielaviopsis species e.g. Thielaviopsis basicola
  • Thielaviopsis species e.g. Thielaviopsis basicola
  • ear and panicle diseases caused, for example, by Alternaria species, (e.g. Alternaria spp.), Aspergillus species (e.g. Aspergillus flavus), Cladosporium species (e.g. Cladosporium cladosporioides, Claviceps species (e.g. Claviceps purpurea), Fusarium species, (e.g. Fusarium culmorum), Gibberella species (e.g. Gibberella zeae), Monographella species, (e.g. Monographella nivalis), Stagnospora species, (e.g. Stagnospora nodorum);
  • Alternaria species e.g. Alternaria spp.
  • Aspergillus species e.g. Aspergillus flavus
  • Cladosporium species e.g. Cladosporium cladosporioides
  • Claviceps species e.g. Clavic
  • Sphacelotheca species e.g. Sphacelotheca reiliana
  • Tilletia species e.g. Tilletia caries or Tilletia controversa
  • Urocystis species e.g. Urocystis occulta
  • Ustilago species e.g. Ustilago nuda
  • fruit rot caused, for example, by Aspergillus species (e.g. Aspergillus flavus), Botrytis species (e.g. Botrytis cinerea), Penicillium species (e.g. Penicillium expansum or Penicillium purpurogenum), Rhizopus species (e.g. Rhizopus stolonifer), Sclerotinia species (e.g. Sclerotinia sclerotiorum), Verticilium species (e.g. Verticilium alboatrum) ;
  • Alternaria species e.g. Alternaria brassicicola
  • Aphanomyces species e.g. Aphanomyces euteiches
  • Ascochyta species e.g. Ascochyta lentis
  • Aspergillus species e.g. Aspergillus flavus
  • Cladosporium species e.g. Cladosporium herbarum
  • Cochliobolus species e.g. Cochliobolus sativus (conidial form: Drechslera, Bipolaris Syn: Helminthosporium)
  • Colletotrichum species e.g.
  • Fusarium species e.g. Fusarium culmorum
  • Gibberella species e.g. Gibberella zeae
  • Macrophomina species e.g. Macrophomina phaseolina
  • Microdochium species e.g. Microdochium nivale
  • Monographella species e.g. Monographella nivalis
  • Penicillium species e.g. Penicillium expansum
  • Phoma species e.g. Phoma lingam
  • Phomopsis species e.g. Phomopsis sojae
  • Phytophthora species e.g. Phytophthora cactorum
  • Pyrenophora species e.g.
  • Pyrenophora graminea Pyricularia species (e.g. Pyricularia oryzae), Pythium species (e.g. Pythium ultimum), Rhizoctonia species (e.g. Rhizoctonia solani), Rhizopus species (e.g. Rhizopus oryzae), Sclerotium species (e.g. Sclerotium rolfsii), Septoria species (e.g. Septoria nodorum), Typhula species (e.g. Typhula incarnate), Verticillium species (e.g. Verticillium dahlia);
  • Pyricularia species e.g. Pyricularia oryzae
  • Pythium species e.g. Pythium ultimum
  • Rhizoctonia species e.g. Rhizoctonia solani
  • Rhizopus species e.g. Rhizopus oryzae
  • Sclerotium species e.g. Sclerotium rolfsi
  • Nectria species e.g. Nectria galligena
  • wilt diseases caused, for example, by Monilinia species (e.g. Monilinia laxa);
  • Exobasidium species e.g. Exobasidium vexans
  • Taphrina species e.g. Taphrina deformans
  • degenerative diseases in woody plants caused, for example, by Esca species (e.g. Phaeomoniella chlamydospora, Phaeoacremonium aleophilum or Fomitiporia mediterranea), Ganoderma species (e.g. Ganoderma boninense);
  • Esca species e.g. Phaeomoniella chlamydospora, Phaeoacremonium aleophilum or Fomitiporia mediterranea
  • Ganoderma species e.g. Ganoderma boninense
  • Botrytis species e.g. Botrytis cinerea
  • Rhizoctonia species e.g. Rhizoctonia solani
  • Helminthosporium species e.g. Helminthosporium solani
  • Xanthomonas species e.g. Xanthomonas campestris pv. Oryzae
  • Pseudomonas species e.g. Pseudomonas syringae pv. Lachrymans
  • Erwinia species e.g. Erwinia amylovora
  • the method for controlling unwanted microorganisms may be used to protect seeds from phytopathogenic microorganisms, such as fungi.
  • seed(s) include dormant seed, primed seed, pregerminated seed and seed with emerged roots and leaves.
  • the present invention also relates to a method for protecting seeds and/or crops from unwanted microorganisms, such as bacteria or fungi, which comprises the step of treating the seeds with one or more compounds of formula (I) or a composition comprising thereof.
  • the treatment of seeds with the compound(s) of formula (I) or a composition comprising thereof not only protects the seeds from phytopathogenic microorganisms, but also the germinating plants, the emerged seedlings and the plants after emergence.
  • the seeds treatment may be performed prior to sowing, at the time of sowing or shortly thereafter.
  • the seeds treatment may be performed as follows: the seeds may be placed into a mixer with a desired amount of compound(s) of formula (I) or a composition comprising thereof (either as such or after dilution), the seeds and the compound(s) of formula (I) or the composition comprising thereof are mixed until a homogeneous distribution on seeds is achieved. If appropriate, the seeds may then be dried.
  • the invention also relates to seeds treated with one or more compounds of formula (I) or a composition comprising thereof.
  • treated seeds allows not only protecting the seeds before and after sowing from unwanted microorganisms, such as phytopathogenic fungi, but also allows protecting the germinating plants and young seedlings emerging from said treated seeds.
  • a large part of the damage to crop plants caused by harmful organisms is triggered by the infection of the seeds before sowing or after germination of the plant. This phase is particularly critical since the roots and shoots of the growing plant are particularly sensitive, and even small damage may result in the death of the plant.
  • the present invention also relates to a method for protecting seeds, germinating plants and emerged seedlings, more generally to a method for protecting crop from phytopathogenic microorganisms, which comprises the step of using seeds treated by one or more compounds of formula (I) or a composition comprising thereof.
  • the seed is treated in a state in which it is sufficiently stable for no damage to occur in the course of treatment.
  • seeds can be treated at any time between harvest and shortly after sowing. It is customary to use seeds which have been separated from the plant and freed from cobs, shells, stalks, coats, hairs or the flesh of the fruits. For example, it is possible to use seeds which have been harvested, cleaned and dried down to a moisture content of less than 15% by weight. Alternatively, it is also possible to use seeds which, after drying, for example, have been treated with water and then dried again, or seeds just after priming, or seeds stored in primed conditions or pre-germinated seeds, or seeds sown on nursery trays, tapes or paper.
  • the amount of compound(s) of formula (I) or composition comprising thereof applied to the seed is typically such that the germination of the seed is not impaired, or that the resulting plant is not damaged. This must be ensured particularly in case the active ingredients would exhibit phytotoxic effects at certain application rates.
  • the intrinsic phenotypes of transgenic plants should also be taken into consideration when determining the amount of compound(s) of formula (I) or composition comprising thereof to be applied to the seed in order to achieve optimum seed and germinating plant protection with a minimum amount of compound(s) of formula (I) or composition comprising thereof being employed.
  • the compounds of the formula (I) can be applied, as such, directly to the seeds, i.e. without the use of any other components and without having been diluted, or a composition comprising the compounds of formula (I) can be applied.
  • the compositions are applied to the seed in any suitable form.
  • suitable formulations include solutions, emulsions, suspensions, powders, foams, slurries or combined with other coating compositions for seed, such as film forming materials, pelleting materials, fine iron or other metal powders, granules, coating material for inactivated seeds, and also ULV formulations.
  • the formulations may be ready-to-use formulations or may be concentrates that need to be diluted prior to use.
  • formulations are prepared in a known manner, for instance by mixing the active ingredient or mixture thereof with customary additives, for example customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins, and also water.
  • customary additives for example customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins, and also water.
  • These formulations are prepared in a known manner, by mixing the active ingredients or active ingredient combinations with customary additives, for example customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins, and also water.
  • customary additives for example customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins, and also water.
  • Useful dyes which may be present in the seed dressing formulations are all dyes which are customary for such purposes. It is possible to use either pigments, which are sparingly soluble in water, or dyes, which are soluble in water. Examples include the dyes known by the names Rhodamine B, C.l. Pigment Red 1 12 and C.l. Solvent Red 1 .
  • Useful wetting agents which may be present in the seed dressing formulations are all substances which promote wetting and which are conventionally used for the formulation of active agrochemical ingredients. Usable with preference are alkylnaphthalenesulphonates, such as diisopropyl- or diisobutylnaphthalenesulphonates.
  • Useful dispersants and/or emulsifiers which may be present in the seed dressing formulations are all nonionic, anionic and cationic dispersants conventionally used for the formulation of active agrochemical ingredients. Usable with preference are nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants.
  • Useful nonionic dispersants include especially ethylene oxide/propylene oxide block polymers, alkylphenol polyglycol ethers and tristryrylphenol polyglycol ether, and the phosphated or sulphated derivatives thereof.
  • Suitable anionic dispersants are especially lignosulphonates, polyacrylic acid salts and arylsulphonate/formaldehyde condensates.
  • Antifoams which may be present in the seed dressing formulations are all foam-inhibiting substances conventionally used for the formulation of active agrochemical ingredients. Silicone antifoams and magnesium stearate can be used with preference.
  • Preservatives which may be present in the seed dressing formulations are all substances usable for such purposes in agrochemical compositions.
  • Examples include dichlorophene and benzyl alcohol hemiformal.
  • Secondary thickeners which may be present in the seed dressing formulations are all substances usable for such purposes in agrochemical compositions. Preferred examples include cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica.
  • Adhesives which may be present in the seed dressing formulations are all customary binders usable in seed dressing products. Preferred examples include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose.
  • the compounds of the formula (I) and the compositions comprising thereof are suitable for protecting seeds of any plant variety which is used in agriculture, in greenhouses, in forests or in horticulture.
  • the seed is that of cereals (such as wheat, barley, rye, millet, triticale, and oats), oilseed rape, maize, cotton, soybean, rice, potatoes, sunflower, beans, coffee, peas, beet (e.g. sugar beet and fodder beet), peanut, vegetables (such as tomato, cucumber, onions and lettuce), lawns and ornamental plants.
  • cereals such as wheat, barley, rye, millet, triticale, and oats
  • oilseed rape maize
  • cotton soybean
  • rice potatoes
  • sunflower beans
  • coffee peas
  • beet e.g. sugar beet and fodder beet
  • peanut such as tomato, cucumber, onions and lettuce
  • the compounds of formula (I) or the compositions comprising thereof can be used for treating transgenic seeds, in particular seeds of plants capable of expressing a protein which acts against pests, herbicidal damage or abiotic stress, thereby increasing the protective effect. Synergistic effects may also occur in interaction with the substances formed by expression.
  • the compound of the invention can be applied as such, or for example in the form of as ready-to-use solutions, emulsions, water- or oil-based suspensions, powders, wettable powders, pastes, soluble powders, dusts, soluble granules, granules for broadcasting, suspoemulsion concentrates, natural products impregnated with the compound of the invention, synthetic substances impregnated with the compound of the invention, fertilizers or microencapsulations in polymeric substances.
  • Application is accomplished in a customary manner, for example by watering, spraying, atomizing, broadcasting, dusting, foaming, spreading-on and the like. It is also possible to deploy the compound of the invention by the ultra-low volume method, via a drip irrigation system or drench application, to apply it in-furrow or to inject it into the soil stem or trunk. It is further possible to apply the compound of the invention by means of a wound seal, paint or other wound dressing.
  • the effective and plant-compatible amount of the compound of the invention which is applied to the plants, plant parts, fruits, seeds or soil will depend on various factors, such as the compound/composition employed, the subject of the treatment (plant, plant part, fruit, seed or soil), the type of treatment (dusting, spraying, seed dressing), the purpose of the treatment (curative and protective), the type of microorganisms, the development stage of the microorganisms, the sensitivity of the microorganisms, the crop growth stage and the environmental conditions.
  • the application rates can vary within a relatively wide range, depending on the kind of application.
  • the application rate may range from 0.1 to 10 000 g/ha, preferably from 10 to 1000 g/ha, more preferably from 50 to 300 g/ha (in the case of application by watering or dripping, it is even possible to reduce the application rate, especially when inert substrates such as rockwool or perlite are used).
  • the application rate may range from 0.1 to 200 g per 100 kg of seeds, preferably from 1 to 150 g per 100 kg of seeds, more preferably from 2.5 to 25 g per 100 kg of seeds, even more preferably from 2.5 to 12.5 g per 100 kg of seeds.
  • the application rate may range from 0.1 to 10 000 g/ha, preferably from 1 to 5000 g/ha.
  • the compound and the composition of the invention may also be used in the protection of materials, especially for the protection of industrial materials against attack and destruction by unwanted microorganisms.
  • the compound and the composition of the invention may be used as antifouling compositions, alone or in combinations with other active ingredients.
  • Industrial materials in the present context are understood to mean inanimate materials which have been prepared for use in industry.
  • industrial materials which are to be protected from microbial alteration or destruction may be adhesives, glues, paper, wallpaper and board/cardboard, textiles, carpets, leather, wood, fibers and tissues, paints and plastic articles, cooling lubricants and other materials which can be infected with or destroyed by microorganisms.
  • Parts of production plants and buildings, for example cooling-water circuits, cooling and heating systems and ventilation and air-conditioning units, which may be impaired by the proliferation of microorganisms may also be mentioned within the scope of the materials to be protected.
  • Industrial materials within the scope of the present invention preferably include adhesives, sizes, paper and card, leather, wood, paints, cooling lubricants and heat transfer fluids, more preferably wood.
  • the compound and the composition of the invention may prevent adverse effects, such as rotting, decay, discoloration, decoloration or formation of mould.
  • the compound and the composition of the invention may also be used against fungal diseases liable to grow on or inside timber.
  • Timber means all types of species of wood, and all types of working of this wood intended for construction, for example solid wood, high-density wood, laminated wood, and plywood.
  • the compound and the composition of the invention may be used to protect objects which come into contact with saltwater or brackish water, especially hulls, screens, nets, buildings, moorings and signaling systems, from fouling.
  • Storage goods are understood to mean natural substances of vegetable or animal origin or processed products thereof which are of natural origin, and for which long-term protection is desired.
  • Storage goods of vegetable origin for example plants or plant parts, such as stems, leaves, tubers, seeds, fruits, grains, may be protected freshly harvested or after processing by (pre)drying, moistening, comminuting, grinding, pressing or roasting.
  • Storage goods also include timber, both unprocessed, such as construction timber, electricity poles and barriers, or in the form of finished products, such as furniture.
  • Storage goods of animal origin are, for example, hides, leather, furs and hairs.
  • the compound and the composition of the invention may prevent adverse effects, such as rotting, decay, discoloration, decoloration or formation of mould.
  • Microorganisms capable of degrading or altering industrial materials include, for example, bacteria, fungi, yeasts, algae and slime organisms.
  • the compound and the composition of the invention preferably act against fungi, especially moulds, wood-discoloring and wood-destroying fungi ( Ascomycetes , Basidiomycetes, Deuteromycetes and Zygomycetes), and against slime organisms and algae.
  • microorganisms of the following genera Alternaria, such as Alternaria tenuis ; Aspergillus, such as Aspergillus niger, Chaetomium, such as Chaetomium globosum ; Coniophora, such as Coniophora puetana ; Lentinus, such as Lentinus tigrinus ; Penicillium, such as Penicillium glaucum ; Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans Sclerophoma, such as Sclerophoma pityophila Trichoderma, such as Trichoderma viride Ophiostoma spp., Ceratocystis spp., Humicola spp., Petriella spp., Trichurus spp., Coriolus spp., Gloeophyllum spp., Pleurotus spp., Por
  • logP values were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a reversed-phase column (C 18), using the method described below :
  • Method A temperature: 40 °C ; mobile phases : 0.1 % aqueous formic acid and acetonitrile ; linear gradient from 10% acetonitrile to 95% acetonitrile;
  • Calibration was carried out using unbranched alkan-2-ones (comprising 3 to 16 carbon atoms) with known logP values (determination of the logP values by the retention times using linear interpolation between two successive alkanones). lambda-max-values were determined using UV-spectra from 200 nm to 400 nm and the peak values of the chromatographic signals.
  • A is connected to L2 of formula (I) via the bonds identified with“*” and A is connected to the NiSO2 moiety of formula (I) via the bonds identified with“#”.
  • Table 1 b illustrates in a non-limiting manner an example of a N-oxide compound of formula (I) according to the invention :
  • logP is defined as for table 1a.
  • Table 1 c illustrates in a non-limiting manner an example of a compound of formula (li) according to the invention :
  • logP is defined as for table 1a.
  • Table 1d illustrates in a non-limiting manner examples of N-oxide compounds of formula (li) according to the invention :
  • logP is defined as for table 1a
  • Table 2 illustrates in a non-limiting manner an example of a compound of formula (Ilia) according to the invention :
  • the GCMS retention times are determined on a DB17ms (15m*0.25pm*0.25pm) column using a 30°C/min gradient from 40°C to 310°C and 1 ,5mL/min He gaz flow.
  • A is connected to L 2 of formula (Ilia) via the bond identified with“*” and A is connected to the N-SO2 moiety of formula (Ilia) via the bond identified with
  • Table 3 illustrates in a non-limiting manner an example of a compound of formula (VII) according to the invention :
  • logP is defined as for table 1a.
  • Table 4 illustrates in a non-limiting manner an example of a compound of formula (X) according to the invention :
  • logP is defined as for table 1a.
  • Table 5 illustrates in a non-limiting manner an example of a compound of formula (Xla) according to the invention :
  • logP is defined as for table 1a.
  • Table 6 provides the NMR data ( 1 H) of some compounds disclosed in tables 1a, 1 b, 1 c, 1d, 2, 3, 4 and 5.
  • the 1 H-NMR data of selected examples are stated in the form of 1 H-NMR peak lists. For each signal peak, the d value in ppm and the signal intensity in brackets are listed.
  • Intensity of sharp signals correlates with the height of the signals in a printed example of a NMR spectrum in cm and shows the real relations of signal intensities. From broad signals several peaks or the middle of the signal and their relative intensity in comparison to the most intensive signal in the spectrum can be shown.
  • the 1 H-NMR peak lists are similar to classical 1 H-NMR prints and contain therefore usually all peaks, which are listed at classical NMR-interpretation. Additionally they can show like classical 1 H-NMR prints signals of solvents, stereoisomers of the target compounds, which are also object of the invention, and/or peaks of impurities.
  • peaks of stereoisomers of the target compounds and/or peaks of impurities have usually on average a lower intensity than the peaks of target compounds (for example with a purity >90%).
  • Such stereoisomers and/or impurities can be typical for the specific preparation process. Therefore their peaks can help to recognize the reproduction of the preparation process via“side-products-fingerprints”.
  • An expert who calculates the peaks of the target compounds with known methods (MestreC, ACD- simulation, but also with empirically evaluated expectation values), can isolate the peaks of the target compounds as needed optionally using additional intensity filters. This isolation would be similar to relevant peak picking at classical 1 H-NMR interpretation.
  • Preparation example 2 preparation of 4,4-difluoro-1-(8-fluoroquinolin-3-yl)-3,3-dimethyl-3,4-dihydro-1 /-/- pyrido[3,2-c][1 ,2]thiazine 2,2-dioxide (compound 1.08)
  • Step 1 preparation of methyl 3-[(8-fluoroquinolin-3-yl)amino]pyridine-2-carboxylate
  • 45 mg (0.04 mmol) of tris(dibenzylideneacetone)dipalladium(0), 85 mg (0.14 mmol) of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene and 0.75 g (2.30 mmol) of cesium carbonate were added under argon atmosphere.
  • Step 2 preparation of methyl 3-[(8-fluoroquinolin-3-yl)(methylsulfonyl)amino]pyridine-2-carboxylate
  • a solution of lithium bis(trimethylsilyl)amide (6.73 ml_, 1.0 M in tetrahydrofuran, 6.73 mmol) was added to a solution of 2.0 g (6.72 mmol) of methyl 3-[(8-fluoroquinolin-3-yl)amino]pyridine-2-carboxylate in 37 mL tetrahydrofuran at 0 °C.
  • Step 4 preparation of 1-(8-fluoroquinolin-3-yl)-3,3-dimethyl-1 /-/-pyrido[3,2-c][1 ,2]thiazin-4(3/-/)-one 2,2- dioxide (compound 1.05)
  • Step 5 preparation of 4,4-difluoro-1-(8-fluoroquinolin-3-yl)-3,3-dimethyl-3,4-dihydro-1 /-/-pyrido[3,2- c][1 ,2]thiazine 2,2-dioxide (compound 1.08)
  • the reaction mixture was stirred at 80 °C for 24 hours.
  • the reaction mixture was cooled to 0 °C, diluted by ethyl acetate and quenched with a slow addition of an aqueous saturated solution of sodium bicarbonate.
  • the aqueous phase was extracted twice with ethyl acetate.
  • the combined organic extracts were washed with water, brine, dried over magnesium sulfate and concentrated under reduced pressure.
  • Step 1 preparation of 1-(8-fluoroquinolin-3-yl)-3,3,4-trimethyl-3,4-dihydro-1 /-/-pyrido[3,2-c][1 ,2]thiazin-4-ol 2,2-dioxide (compound 1.10)
  • Step 2 preparation of 4-(benzyloxy)-1-(8-fluoroquinolin-3-yl)-3,3,4-trimethyl-3,4-dihydro-1 /-/-pyrido[3,2- c][1 ,2]thiazine 2,2-dioxide (compound 1.28)
  • Preparation example 4 preparation of 1-(8-fluoro-1-oxidoquinolin-3-yl)-4-methoxy-3,3,4-trimethyl-3,4- dihydro-1 H-pyrido[3,2-c][1 ,2]thiazine 2,2-dioxide (compound 1.40) and 1-(8-fluoroquinolin-3-yl)-4-methoxy- 3,3,4-trimethyl-3,4-dihydro-1 H-pyrido[3,2-c][1 ,2]thiazine 2,2,5-trioxide (compound 1.38)
  • Emulsifier 1 pi of Tween ® 80 per mg of tested compound
  • the tested compounds were made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone/ /Tween ® 80 and then diluted in water to the desired concentration.
  • the young plants of radish or cabbage were treated by spraying the tested compound prepared as described above. Control plants were treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/ Tween ® 80.
  • the plants were contaminated by spraying the leaves with an aqueous suspension of Alternaria brassicae spores.
  • the contaminated radish or cabbage plants were incubated for 6 days at 20°C and at 100% relative humidity.
  • Emulsifier 1 mI of Tween ® 80 per mg of tested compound
  • the tested compounds were made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone/ /Tween ® 80 and then diluted in water to the desired concentration.
  • the young plants of gherkin were treated by spraying the tested compound prepared as described above. Control plants were treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/ Tween ® 80.
  • the plants were contaminated by spraying the leaves with an aqueous suspension of Botrytis cinerea spores.
  • the contaminated gherkin plants were incubated for 4 to 5 days at 17°C and at 90% relative humidity.
  • the test was evaluated 4 to 5 days after the inoculation. 0% means an efficacy which corresponds to that of the control plants while an efficacy of 100% means that no disease was observed.
  • Emulsifier 1 mI of Tween ® 80 per mg of tested compound
  • the tested compound s were made soluble and homogenized in a mixture of Dimethyl sulfoxide/Acetone/ /Tween ® 80 and then diluted in water to the desired concentration.
  • the young plants of gherkin were treated by spraying the tested compound prepared as described above. Control plants were treated only with an aqueous solution of Acetone/Dimethyl sulfoxide/ Tween ® 80.
  • the plants were contaminated by spraying the leaves with an aqueous suspension of Sphaerotheca fuliginea spores.
  • the contaminated gherkin plants were incubated for 8 days at 20°C and at 70-80% relative humidity.
  • Culture medium 14.6g anhydrous D-glucose (VWR), 7.1 g Mycological Peptone (Oxoid), 1.4g granulated Yeast Extract (Merck), QSP 1 liter
  • Inoculum spores suspension
  • the compounds to be tested were solubilized in DMSO and the solution used to prepare the required range of concentrations.
  • the final concentration of DMSO used in the assay was ⁇ 1 %.
  • a spore suspension of C. lindemuthianum was prepared and diluted to the desired spore density.
  • the compounds were evaluated for their ability to inhibit spores germination and mycelium growth in liquid culture assay.
  • the compounds were added in the desired concentration to the culture medium with spores. After 6 days incubation, fungi-toxicity of compounds was determined by spectrometric measurement of mycelium growth. Inhibition of fungal growth was determined by comparing the absorbance values in wells containing the tested compound with the absorbance in control wells without tested compound.
  • Culture medium 14.6g anhydrous D-glucose (VWR), 7.1 g Mycological Peptone (Oxoid), 1.4g granulated Yeast Extract (Merck), QSP 1 liter
  • Inoculum spore suspension
  • the compounds to be tested were solubilized in DMSO and the solution used to prepare the required range of concentrations.
  • the final concentration of DMSO used in the assay was ⁇ 1 %.
  • a spore suspension of P. oryzae was prepared and diluted to the desired spore density.
  • the compounds were evaluated for their ability to inhibit spore germination and mycelium growth in liquid culture assay.
  • the compounds were added in the desired concentration to the culture medium with spores. After 5 days incubation, fungi-toxicity of compounds was determined by spectrometric measurement of mycelium growth. Inhibition of fungal growth was determined by comparing the absorbance values in wells containing the compounds to be tested with the absorbance in control wells without tested compound.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne des composés fongicides actifs, plus spécifiquement des benzosultames et analogues, des procédés et intermédiaires de leur préparation, et leur utilisation en tant que composés fongicides actifs, particulièrement sous la forme de compositions fongicides. La présente invention se rapporte également à des procédés pour la lutte contre les champignons phytopathogènes de plantes, utilisant ces composés ou ces compositions comprenant ces derniers.
PCT/EP2018/086551 2017-12-22 2018-12-21 Benzosultames hétérocycliques et analogues WO2019122320A1 (fr)

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Citations (3)

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JP2008088139A (ja) 2006-10-05 2008-04-17 Sankyo Agro Kk ３−置換キノリン化合物
JP2014221747A (ja) 2013-05-14 2014-11-27 日本曹達株式会社 含窒素ヘテロ環化合物および農園芸用殺菌剤
JP2017001998A (ja) 2015-06-12 2017-01-05 アグロカネショウ株式会社 １，４−ベンゾチアジン−１，３−ジオン又は−１，１，３−トリオン誘導体およびこれを有効成分とする殺菌剤

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JP2008088139A (ja) 2006-10-05 2008-04-17 Sankyo Agro Kk ３−置換キノリン化合物
JP2014221747A (ja) 2013-05-14 2014-11-27 日本曹達株式会社 含窒素ヘテロ環化合物および農園芸用殺菌剤
JP2017001998A (ja) 2015-06-12 2017-01-05 アグロカネショウ株式会社 １，４−ベンゾチアジン−１，３−ジオン又は−１，１，３−トリオン誘導体およびこれを有効成分とする殺菌剤

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SAUL PATAI; AVI RAPPOPORT: "The Chemistry of Functional Groups - The Chemistry of sulphonic acids, esters and their derivatives", 1991, WILEY-INTERSCIENCE, pages: 851 - 878

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TW201930316A (zh) 2019-08-01

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