MICROBIOCIDAL OXADIAZOL DERIVATIVES

专利摘要:
Compounds of formula (I),(I)wherein the substituents are as defined in claim 1, useful as pesticides, especially as fungicides.
公开号:BR112019018238A2
申请号:R112019018238-1
申请日:2018-03-01
公开日:2020-06-23
发明作者:James Hoffman Thomas；Thomas James Hoffman；Stierli Daniel；Daniel Stierli；Pitterna Thomas；Thomas Pitterna；Rajan Ramya；Ramya Rajan
申请人:Syngenta Participations Ag；
IPC主号:

专利说明:

[0001] [0001] The present invention relates to microbiocidal oxadiazole derivatives, e.g., as active ingredients, which have microbiocidal activity, in particular fungicidal activity. The invention also relates to agrochemical compositions comprising at least one of the oxadiazole derivatives, to processes for preparing these compounds and to uses of the oxadiazole derivatives or compositions in agriculture or horticulture to control or prevent plant infestation, food crops harvested, seeds or non-living materials by phytopathogenic microorganisms, preferably fungi.
[0002] [0002] WO 2015/185485 describes the use of substituted oxadiazoles to combat phytopathogenic fungi.
[0003] [0003] In accordance with the present invention, a compound of Formula (1) is provided: R DAS
[0004] [0004] Surprisingly, it has been discovered that the new compounds of Formula (1) have, for practical purposes, a very advantageous level of biological activity to protect plants against diseases that are caused by fungi.
[0005] [0005] In accordance with a second aspect of the invention, an agrochemical composition comprising a fungicidally effective amount of a compound of Formula (1) is provided. Such an agricultural composition may further comprise at least one additional active ingredient and / or an agrochemical acceptable diluent or carrier.
[0006] [0006] According to a third aspect of the invention, a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms is provided, wherein a fungicidal effective amount of a compound of Formula (1) or a composition comprising this compound as an active ingredient, it is applied to plants, parts of them or their locus.
[0007] [0007] According to a fourth aspect of the invention, the use of a compound of Formula (TI) as a fungicide is provided. In accordance with this particular aspect of the invention, use may exclude methods for treating the human or animal body by surgery or therapy.
[0008] [0008] As used herein, the term "halogen" or "halo" refers to fluorine (fluorine), chlorine (chlorine), bromine (bromine) or iodine (iodine), preferably fluorine, chlorine or bromine.
[0009] [0009] As used herein, cyan means a -CN group.
[0010] [0010] As used herein, the term "hydroxyl" or "hydroxy" means an -OH group.
[0011] [0011] As used herein, amino designates an -NH> group.
[0012] [0012] As used herein, acyl means a group - C (0) CH :.
[0013] [0013] As used herein, formyl means a group - C (O) H.
[0014] [0014] As used herein, the term "C1.5 alkyl" refers to a radical of a straight or branched hydrocarbon chain consisting only of carbon and hydrogen atoms, containing no unsaturation, having from one to six carbon atoms , and which is linked to the rest of the molecule by a single bond. C1.4 alkyl, C1.3 alkyl and C1.7 alkyl must be interpreted accordingly. Examples of C1 alkyls include, but are not limited to, methyl, ethyl , n-propyl, l-methylethyl (isopropyl), n-butyl and l-dimethylethyl (t-butyl) .A “C1. C7 alkylene” group refers to the corresponding definition of C1.2 alkyl,
[0015] [0015] As used herein, the term "C1.4 alkoxy" refers to a radical of the formula -ORx, where Rx is a C1-alkyl radical as defined in general above. The terms C1-3 alkoxy and C1> 7 alkoxy must be interpreted accordingly. Examples of C1.4 alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy and t-butoxy.
[0016] [0016] As used herein, the term "C1-.3 haloalkyl" refers to a C1.3 alkyl radical as defined in general above, substituted with one or more equal or different halogen atoms. Examples of C1.3 haloalkyls include, but are not limited to, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl and 3,3,3-trifluoropropyl.
[0017] [0017] As used herein, the term "C> .5" alkenyl "refers to a radical group of a straight or branched hydrocarbon chain consisting only of carbon and hydrogen atoms, containing at least one double bond that may have the configuration (E) or (Z), having two to six carbon atoms, which is linked to the rest of the molecule by a single bond. C3-6 alkenyl, C3.5 alkenyl, C2.4 alkenyl and C7; 3 alkenyl should be interpreted accordingly. Examples of C 1-4 alkenyls include, but are not limited to, prop-1-enyl, allyl (prop-2-enyl) and but-1-enyl.
[0018] [0018] As used herein, the term "haloalkenyl C3.5" refers to a C3.6 alkenyl radical as defined in general replaced by one or more equal or different halogen atoms. Haloalkenyl C3.4 should be interpreted in accordance.
[0019] [0019] As used herein, the term "C2.4 alken-Oxy" refers to a radical of the formula -OR., Where Rx is a C2.4 alkenyl radical as defined in general above.
[0020] [0020] As used herein, the term "C> .5" alkynyl refers to a radical group of a straight or branched hydrocarbon chain consisting only of carbon and hydrogen atoms, containing at least one triple bond, having two to six carbon atoms, and which is linked to the rest of the molecule by a single bond. C3.kynyl and C2-4 alkynyl must be interpreted accordingly. Examples of Cr6 alkynyl include, but are not limited to, prop-1-inyl , propargyl (prop-2-inyl).
[0021] [0021] As used herein, the term "alkyn C2.4-Oxy" refers to a radical of the formula -OR., Where Rx is a C2.4 alkynyl radical as defined in general above.
[0022] [0022] As used herein, the term "C1-4 alkoxy-C1-4 alkyl" refers to the radical of the formula Ry-O0-Rx- where Ry is a C1.4 alkyl radical as defined in general above, and Rx is a C1.4 alkylene radical as defined in general above.
[0023] [0023] As used herein, the term "C1-4 hydroxyalkyl" refers to a C1.4 alkyl radical as defined in general above, substituted by one or more hydroxy groups. The term "hydroxyalkyl C1.2" must be interpreted accordingly.
[0024] [0024] As used herein, the term "C1.7 cyanoalkyl" refers to a C1.2 alkyl radical as defined in general above replaced by one or more cyano groups.
[0025] [0025] As used herein, the term "C1-4 alkyl carbonyl" refers to a radical of the formula -C (O) Rx where Rx is a C1.4 alkyl radical as defined in general above.
[0026] [0026] As used herein, the term "C13-alkylcarbonyl" refers to a radical of the formula - [C (0)] 2Rx where Rx. is a C1.3 alkyl radical as defined in general above.
[0027] [0027] As used herein, the term "C13 alkyl-carbonyloxyalkyl C1.2" refers to a radical of the formula RyC (0) ORx- where R, y is a C1.3 alkyl radical as defined in general above, and R. is a C1.2 alkylene radical as defined in general above.
[0028] [0028] As used herein, the term "C1.2 alkoxy-C1-2 alkoxy-C1.2 alkyl" refers to a radical of the formula RxOR, OR, -, where Ry and R; are C1.2 alkylene radicals as defined in general above, and Rx. is a C1.2 alkyl radical as defined in general above.
[0029] [0029] As used herein, the term "C13-aminocarbonyl alkoxy" refers to a radical of the formula RxONHC (0O) -, where Rx is a C1.3 alkyl radical as defined in general above.
[0030] [0030] As used herein, the term "N-C1.3-N-alkyl C1-.3-aminocarbonyl" refers to a radical of formula (Rx) (RxO) JNHC (0) - where each Rx is a C13 alkyl radical as generally defined above. As used herein, the term "C1.3-carbonyl alkoxy" refers to a radical of the formula R.OC (0) -, where Rx is a C1-3 alkyl radical as defined in general above.
[0031] [0031] As used herein, the term "C13 alkoxy-C12 carbonylalkyl" refers to a radical of the formula
[0032] [0032] As used herein, the term "C13-dicarbonyl alkoxy" refers to a radical of the formula RxO [C (0)]> -, where Rx. is a C1.3 alkyl radical as defined in general above. The term C1.2-dicarbonyl alkoxy "must be interpreted accordingly.
[0033] [0033] As used herein, the term "C1.2 alkyl-sulfonyl" refers to a radical of the formula R.S (0); -, where Rx is a C1.2 alkyl radical as defined in general above.
[0034] [0034] As used herein, the term "N-C1-.3-amino" refers to a radical of formula R.NH- where Rx is a C1.3 alkyl radical as defined in general above.
[0035] [0035] As used herein, the term "N, N-dialkyl C1.2-amino" refers to a radical of formula R «(RJ) N- where Rx is a C1.2 alkyl radical as defined in general above.
[0036] [0036] As used herein, the term "N-alkyl C1.2-aminosulfonyl" "refers to a radical of the formula R.NH S (0): - where Rx is a C1.2 alkyl radical as defined in general above.
[0037] [0037] As used herein, the term "N, N-dialkyl C1.2-aminosulfonyl" refers to a radical of formula Rx (Rx) NS (0) 2- where each Rx is independently a C1.- alkyl radical 2 as defined in general above.
[0038] [0038] As used herein, the term "C13-aminocarbonyl alkyl" refers to a radical of the formula R.NHC (0O) - where Rx. is a C1.3 alkyl radical as defined in general above.
[0039] [0039] As used herein, the term "N, N-dialkyl C1.3-aminocarbonyl" refers to a radical of formula (R «) RkNHC (0) - where each Rx is independently a C1.3 alkyl radical such as generally defined above.
[0040] [0040] As used herein, the term "N-C1.3 alkyl-aminodicarbonyl" refers to a radical of the formula RxkNH [C (0)] 2-where Rx is a C1.3 alkyl radical as defined in general above.
[0041] [0041] As used herein, the term "N, N-dialkyl C1.3-aminodicarbonyl" refers to a radical of formula (Rx) R «NH [C (0)] 2- where each Rx is independently a radical C1.3 alkyl as defined in general above. The term N, N-dialkyl Cr2-aminodicarbonyl should be interpreted accordingly.
[0042] [0042] As used herein, the term "N, N-dialkyl C1.3-aminocarbonylalkyl C1.2" refers to a radical of formula (Rx) R «NHC (O0) Ry- where each Rx is independently a radical C1.3 alkyl as defined in general above, and R, is a C1.2 alkylene radical as defined in general above.
[0043] [0043] As used herein, the term "C3.5 cycloalkyl" refers to a radical of a stable monocyclic ring that is saturated or partially unsaturated, and contains 3 to 6 carbon atoms. C3.5 cycloalkyl and C3 cycloalkyl should Examples of C3.6 cycloalkyls include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclopenten-1-yl, cyclopenten-3-yl, and cyclohexen-3-yl.
[0044] [0044] As used herein, the term "C3-6 cycloalkyl C1.2 alkyl" refers to a C3.6 cycloalkyl ring as defined above attached to the rest of the molecule by a C12 alkylene radical as defined above. Examples of C3-6 cycloalkyl C1.3 alkyls include, but are not limited to, cyclopropylmethyl and cyclobutylethyl.
[0045] [0045] As used herein, the term "C1.7 phenylalkyl" refers to a phenyl ring attached to the rest of the molecule by a C1-2 alkylene radical as defined above. Examples of C1.2 phenylalkyl include, but are not limited to, benzyl.
[0046] [0046] As used herein, the term "heteroaryl" generally refers to a radical of a 5- or 6-membered monocyclic aromatic ring comprising 1, 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur. The heteroaryl radical is linked to the rest of the molecule through a carbon atom or heteroatom. Examples of heteroaryls include, but are not limited to, furyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl, pyridyl and indolyl.
[0047] [0047] As used herein, the term "C1-2 heteroarylalkyl" refers to a heteroaryl as defined in general above, linked to the rest of the molecule by a C1-2 alkylene radical as defined above.
[0048] [0048] As used herein, the term "heterocyclyl" or "heterocyclic (a)" generally refers to a stable, saturated or partially saturated, 4- to 6-membered, non-aromatic monocyclic ring comprising 1, 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur. The heterocyclyl radical can be linked to the rest of the molecule through a carbon atom or heteroatom. Examples of heterocyclyl include, but are not limited to, azetidinyl, oxetanyl, pyrrolidyl, tetrahydrofuryl,
[0049] [0049] As used herein, the term "heterobicyclyl" or "heterobicyclic (a)" refers to a radical of a stable, saturated, partially "saturated or aromatic 7 to 9 membered ring or saturated spirocyclic ring containing 1 nitrogen , which comprises 1 or 2 additional members in the ring individually selected from nitrogen, oxygen and sulfur. The heterobicyclyl radical is linked to the rest of the molecule through a nitrogen atom. Examples of heterobicycles include, but are not limited to, pyrrolopyridine, benzimidazole.
[0050] [0050] The presence of one or more possible asymmetric carbon atoms in a compound of Formula (IT) means that the compounds can occur in chiral isomeric forms, that is, enantiomeric or diastereomeric forms. Likewise, atropisomers can occur as a result of restricted rotation around a single bond. Formula (1) is intended to include all of these possible isomeric forms and their mixtures. The present invention includes all of these possible isomeric forms and mixtures thereof for a compound of Formula (1). Likewise, Formula (I) is intended to include all possible tautomers (including tautomerism - “lactam-lactime and keto-enol tautomerism) when present. The present invention includes all possible tautomeric forms for a compound of Formula (1).
[0051] [0051] In each case, the compounds of Formula (1) according to the invention are in the free form, in the oxidized form as an N-oxide, in a covalently hydrated form, or in the form of salt, e.g. in an agronomically usable or agrochemically acceptable salt form.
[0052] [0052] N-oxides are oxidized forms of tertiary amines or oxidized forms of heteroaromatic compounds containing nitrogen. They are described, for example, in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
[0053] [0053] The following list provides definitions, including preferred definitions, for substituents A (A-1, A-2, A-3), Rt, R2, Z (including 21, 22, Z3), R3, R4 , R5 (including Rº, Rb, Re, Rd, Re, R $), D and R7, with reference to the compounds of Formula (1) according to the invention. For any of these substituents, any of the definitions provided below may be combined with any definition of any other substituent provided below or elsewhere in this document.
[0054] [0054] A is selected from A-1, A-2, and A-3. A-1 represents a 2,5-thienyl group, A-2 represents a 2,4-thienyl group, and A-3 represents a 3,5-thienyl group. Preferably, A is A-11.
[0055] [0055] R! and R2 independently represent hydrogen, methyl, ethyl, fluorine, cyano, difluoromethyl or trifluoromethyl. Preferably, R! and Rº independently represent hydrogen or methyl, more preferably R! and R2 both represent hydrogen.
[0056] [0056] Zz is selected from 721, 22 and 723.
[0057] [0057] Z! represents a 4, 5 or 6-membered non-aromatic heterocyclic ring containing 1 nitrogen in the ring, where the heterocyclyl optionally comprises 1 or 2 additional members in the ring independently selected from N, O, S, C (0) and S (0) >, provided that the heterocyclyl cannot contain 2 contiguous atoms selected from O and S, or the heterocyclyl optionally comprises 1 additional member in the NR3 ring, where the heterocyclyl is optionally substituted by 1 or 2 substituents, which can be the same or different, selected from Rº, and in which the heterocyclyl is additionally linked to the rest of the molecule through nitrogen in the ring.
[0058] [0058] Preferably 2! represents a 4-, 5- or 6-membered non-aromatic heterocyclyl containing 1 nitrogen in the ring, where the heterocyclyl optionally comprises 1 additional ring member independently selected from N, O, S, C (0) or S (0), (in in particular, O or C (0)), in which the heterocyclyl is optionally substituted by 1 or 2 substituents, which can be the same or different, selected from Rº, and in which additionally the heterocyclyl is linked to the rest of the molecule through a nitrogen in the ring.
[0059] [0059] More preferably, 2! is selected from: Nao NÃ NON NÃ
[0060] [0060] In certain embodiments of the invention, 722 is optionally substituted by 1 substituent selected from Rº.
[0061] [0061] R3 represents hydrogen, hydroxy, amino, formyl, C1.3 alkyl, C1.3 alkoxy, C1.3-carbonyl alkyl, C1.3-carbonyl alkoxy, N-C1.3-aminocarbonyl alkyl, N, N- dialkyl C1.3-aminocarbonyl, N-alkoxy C1.3-aminocarbonyl, N-alkyl C1.3-N-alkoxy C1.3-aminocarbonyl, alkyl C1.2-sulfonyl, N-alkyl C1-2-aminosulfonyl, N, N-dialkyl C1-2-aminosulfonyl, C1.2-alkyl dicarbonyl, C1-2-dicarbonyl alkoxy, N-C1 alkyl. 2aminodicarbonyl or N, N-N-dialkyl C1.2-aminodicarbonyl.
[0062] [0062] Rº represents cyan, halogen, hydroxy, amino, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, N-methylamino or N, N-dimethylamino. Preferably, Rº is selected from methyl or ethyl.
[0063] [0063] 7th represents a 5- or 6-membered heteroaryl ring containing 1 nitrogen in the ring, where the heteroaryl optionally comprises 1, 2 or 3 additional ring members independently selected from O, S, or N, and where the heteroaryl is optionally substituted by: 1 or 2 substituents selected from Ró, 1 substituent selected from R6, or 1 substituent selected from Rº and 1 substituent selected from Rº, and in which additionally the heteroaryl is linked to the rest of the molecule through nitrogen in the ring;
[0064] [0064] In certain preferred embodiments of the invention, 72º is optionally substituted by 1 or 2 substituents selected from R5, and more preferably it is optionally substituted by a single substituent selected from R5.
[0065] [0065] Preferably, 72º is selected from:
[0066] [0066] More preferably, 2nd is selected from: X “Ns Es do FAITH E A> E NÇZN WE NS where 7º is optionally replaced by: 1 or 2 substituents selected from R5, 1 substituent selected from R6, or 1 substituent selected from Rº and 1 substituent selected from Rº.
[0067] [0067] Rº represents hydroxyl, amino, cyano, halogen, formyl, nitro, C14s alkyl, C14 alkoxy, C3.1 alkenyl, C3.4 alkynyl, C3.4-Oxy alkenyl, C3.4-Oxy alkylene, C1- cyanoalkyl 2, C1-2 haloalkyl, C1.2 hydroxyalkyl, C1.2 alkoxy-C1-2 alkyl, C1.2-alkoxy C1-2 alkoxy, C1.2, N, N-dimethylamino, C1-3-carbonylalkylalkyl C1-2, C1-3alkyl-C1.2-carbonyloxyalkyl, C1-2 N -alkyl-C1-2-aminocarbonylalkyl, C1.2-N-dialkyl-C1.2-aminocarbonylalkyl, C1.2-alkyl, sulfonyl, C1.3- alkyl carbonyl, C1-3 alkyl-dicarbonyl, C1-3 alkoxy-dicarbonyl, N-C1-3 alkyl-aminodicarbonyl or N, N-C1-3 alkyl-aminodicarbonyl; or R5 represents -C (O) N (R2a) (Rº) where:
[0068] [0068] Preferably, R5 is independently selected from hydroxy, amino, cyano, halogen, formyl, nitro, C1.4 alkyl, C1.4 alkoxy, C1.2 haloalkyl, C1 alkoxy. 2-C1.2 alkyl, N, N-dimethylamino, -C (0) O-Rº where Re is C1-1 alkyl, E -C (O) N (Ra) (Rº), where Rº is selected from hydrogen, C1.4 alkyl or C1.4 alkoxy, and Rº is selected from hydrogen or methyl, and Rº is phenyl optionally substituted by 1 or 2 substituents, which can be the same or different, selected from hydroxyl, methyl, methoxy, cyano, fluorine, chlorine or bromine.
[0069] [0069] More preferably, R5 is selected from amino, cyano, chlorine, fluorine, formyl, nitro, methyl, ethyl, difluoromethyl, methoxymethyl, N, N-dimethylamino, methoxycarbonyl, ethoxycarbonyl or n-propoxycarbonyl; or - C (O) N (Ra) (Rº) where Rº is selected from hydrogen, methyl or methoxy and Rº is selected from hydrogen or methyl, and Rº is phenyl optionally substituted by 1 or 2 substituents, which can be the same or different, selected from fluorine, chlorine or bromine.
[0070] [0070] 73 represents a heterobicyclyl which is a fused saturated, partially saturated or aromatic 7 to 9 membered ring or saturated spirocyclic ring system containing 1 nitrogen, wherein the heterobicyclyl optionally comprises 1 or 2 additional members in the ring independently selected from N , O, S, C (0) and S (0)> provided that the heterobicyclyl cannot contain 2 contiguous atoms selected from O and S, where the heterobicyclyl is optionally substituted by 1 substituent selected from R7, and in which additionally the heterobicyclyl is linked to the rest of the molecule through nitrogen in the ring; and Preferably, Z3 represents a heterobicyclyl which is a 9-membered saturated, partially saturated or aromatic fused ring system containing 1 nitrogen, wherein the heterobicyclyl optionally comprises 1 additional member in the ring independently selected from N, O eS, where the heterobicyclyl it is optionally substituted by 1 substituent selected from R /, in which in addition the heterobicyclyl is linked to the rest of the molecule through a nitrogen in the ring.
[0071] [0071] More preferably, Z3 is selected from:
[0072] [0072] R7º is cyan, fluorine, chlorine, amino, hydroxy, methyl, difluoromethyl, trifluoromethyl, methoxy, N, N-dimethylamino, formyl, methylcarbonyl, metoxycarbonyl, N-methylaminocarbonyl or N, N-dimethylaminocarbonyl.
[0073] [0073] Preferably, the compound according to Formula (1) is selected from a compound 1.1 to 1,190 listed in Table T1 (below).
[0074] [0074] Preferably, in a compound according to Formula (1) of the invention: A is A-1l; R! is hydrogen and Rº is hydrogen or methyl; 7 is 7), where 2nd represents a 4, 5 or 6-membered non-aromatic heterocyclyl containing 1 nitrogen in the ring, where the heterocyclyl optionally comprises 1 additional member in the ring independently selected from N, O, S, C (O0) or S (0), (in particular, O or C (0)), in which the heterocyclyl is optionally substituted by 1 or 2 substituents, which can be the same or different, selected from Ri, and in which additionally the heterocyclyl is linked to the rest of the molecule through nitrogen in the ring; and Rº represents cyano, halogen, hydroxy, amino, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, N-methylamino or N, N-dimethylamino.
[0075] [0075] More preferably, A is A-1l; R! and R2 are hydrogen; 7 is 7), where 2! represents a 4, 5 or 6-membered non-aromatic heterocyclyl containing 1 nitrogen in the ring, where the heterocyclyl optionally comprises 1 additional member in the ring independently selected from N, O, S, C (O0) or S (0), (in in particular, O or C (0)), in which the heterocyclyl is optionally substituted by 1 or 2 substituents, which can be the same or different, selected from Ri, and in which additionally the heterocyclyl is linked to the rest of the molecule through nitrogen in the ring; and Rº represents methyl or ethyl.
[0076] [0076] Preferably, in a compound according to Formula (1) of the invention: A is A-1l; R! is hydrogen and Rº is hydrogen or methyl; and z7 is 7, where 7 is selected from: O - jo PA N Ú N RA Q N
[0077] [0077] More preferably, A is A-1l; R! and R2 are hydrogen; and Z7 is 7th, in which 7th is selected from: O = PE q 4 Ore De O
[0078] [0078] Preferably, in a compound according to Formula (1) of the invention: A is A-1l; R! is hydrogen and Rº is hydrogen or methyl; and 7 is 733, where Z represents a heterobicyclyl which is a 9-membered saturated, partially saturated or aromatic fused ring system containing 1 nitrogen, where the heterobicyclyl optionally comprises 1 additional member in the ring independently selected from N, O eS, where the heterobicyclyl is optionally substituted by 1 substituent selected from R /, in which in addition the heterobicyclyl is linked to the rest of the molecule through nitrogen in the ring; Most preferably, A is A-11; R! and R2 are hydrogen; 7 is 73, where Z represents a heterobicyclyl which is a 9-membered saturated, partially saturated or aromatic fused ring system containing 1 nitrogen, where the heterobicyclyl optionally comprises 1 additional member in the ring independently selected from N, O eS, where the heterobicyclyl is optionally substituted by 1 substituent selected from R /, in which in addition the heterobicyclyl is linked to the rest of the molecule through nitrogen in the ring; and R7 is selected from hydroxyl, methoxy, methyl, cyano, fluorine or chlorine.
[0079] [0079] The compounds of the present invention can be enantiomers of the compound of Formula (1) as represented by a Formula (Ta) or a Formula (Ib), wherein R! and R2 are different substituents. >> Jo>% o RA GA: F F
[0080] [0080] It is understood that, when in aqueous media, the compounds of Formula (1) according to the invention may be present in a reversible equilibrium with the corresponding covalently hydrated forms (i.e., the compounds of Formula (I-Ia ) and Formula (I-IIa) as shown below, which can exist in tautomeric form as the compounds of formula (I-Ib) and formula (I-IIb)) in the CF3-oxadiazole motif. This dynamic balance can be important for the biological activity of the compounds of Formula (TI). The designations of A (A-1, A-2, A-3), Ri, R2, Z (including 21, 22, Z3), R3, R4, Rº (including Ra, Rº, Re, Rd, Re, R1 ), D and R7, with respect to the compounds of Formula (I) of the present invention generally apply to compounds of Formula (I-Ia), Formula (I-Ib), Formula (I-IIa), and Formula (I- IIb), as well as the specific disclosures for combinations of A (A-1, A-2, A-3), RI, R2, Z (including 21, 22, Z3), R3, R4, R5 (including Ra , Re, Re, R4, Re, Rf1), D and R7, as shown in Tables
[0081] [0081] The compounds of the present invention can be prepared as shown in the following schemes 1 to 10, in which, unless otherwise specified, the definition of each variable is as defined above for a compound of Formula (1).
[0082] [0082] The compounds of Formula (I) can be prepared from compounds of Formula (II), where X is 0SO0CH; 3, Cl, Br, or I, by treatment with compounds of Formula (III), in presence of a base (eg triethylamine, N, N-diisopropylethylamine, K2C03, NaHCO3, Na2CO3, Cs2CO3, or NaH) in a suitable solvent (eg dimethylacetamide, tetrahydrofuran, 2-methyltetrahydrofuran , acetone, toluene, or acetonitrile) at a temperature between 25 ºC and 110 ºC. In some cases, better reaction performance can be gained by using a catalyst (eg, BusNHSOs, BuaNBr, BuaNT, NaIl, or 4-dimethylaminopyridine) and microwave irradiation. In addition, the compounds of formula (1), can optionally be obtained through a coupling transformation with compounds of formula (III) and compounds of formula (II), where X is OH, through a process that converts -OH in an improved leaving group, such as a -S02CH3 group, for example using methanesulfonyl chloride (C1SO0XMe), before treatment with the compounds of formula (III). For related examples, see: WO 2013/132253, WO 2017/118689, and Garcia, M. et al Org. Biomol. Chem. (2004), 11, 1633. This reaction is shown in Scheme 1.
[0083] [0083] The compounds of Formula (II), where X is halogen, preferably Cl or Br, can be prepared from compounds of Formula (IV) by treatment with a halogen source (eg, N-bromosuccimide (NBS) or N-chlorosuccimide (NCS)) and a radical initiator (eg, (PhCO02) 2 or azobisisobutyronitrile (AIBN)) in a suitable solvent, such as tetrachloromethane, at temperatures between 55 º and 100 ºC in the presence of ultraviolet light. For related examples, see Liu, S. et al Synthesis (2001), 14, 2078, WO 2017/118689, and Kompella, A. et al Org. Proc. Res. Dev. (2012), 16, 1794. This reaction is shown in Scheme 2. "HK A TA, x a
[0084] [0084] Alternatively, compounds of Formula (II), where X is hydrogen, OH, Cl, Br, or I, can be prepared from compounds of Formula (V) by treatment with trifluoroacetic anhydride or trifluoroacetyl halide ( including trifluoroacetyl fluoride, trifluoroacetyl chloride and trifluoroacetyl bromide) in the presence of a base (eg, pyridine or 4-dimethylaminopyridine) in a suitable solvent, (eg, ethyl acetate, tetrahydrofuran, 2 -methyl-tetrahydrofuran, or ethanol), at a temperature between 0 ºC and 75 ºC. For related examples, see WO 2003/028729, WO 2017/055473, and WO 2010/045251. This reaction is shown in Scheme 3. 1 Rº ed Qdo x NH, x N
[0085] [0085] The compounds of Formula (V), where X is hydrogen, OH, or halogen, can be prepared from compounds of Formula (VI) by treatment with a hydroxylamine hydrochloride salt or a hydroxylamine solution in water , in the presence of a base, such as triethylamine or potassium carbonate, in a suitable solvent, such as methanol or ethanol, at a temperature between 0 ºC and 80 ºC. In some cases, better reaction performance can be gained with the use of a catalyst (eg, 8-hydroxyquinoline). For related examples, see Kitamura, S. et al. Chem. Pharm. Bull. (2001), 49, 268, WO 2017/055473 and WO 2013/066838. This reaction is shown in Scheme 4. Ri Ri N. da, r ———> da o x x NH, (VI) (V) Scheme 4
[0086] [0086] The compounds of Formula (VI) can be prepared from compounds of Formula (VII), in which Y is Cl, Br or I, by means of a reaction promoted by a metal with a suitable cyanide reagent, such as such as Pd (0) / Zn (CN)> or CuCN, in a suitable solvent (eg, dimethylformamide or N-methylpyrrolidone) at elevated temperature, between 100 ºC and 120 ºC. For related examples, see US 2007/0155739 and WO 2009/022746. This reaction is shown in Scheme 5.
[0087] [0087] The compounds of Formula (VII), where X is Cl, Br, I or 0S0Me and Y is Cl, Br, I or CN, are commercially available or can be prepared from compounds of Formula (VIII), through treatment with an acid source (eg, hydrochloric acid, hydrobromic acid, or hydroiodic acid), or with a source of halogens (eg, CCU3Br, CCla or 17) in the presence of triphenylphosphine, or with chloride methanesulfonyl (C1ISO0Me), in a suitable solvent, (eg, dichloromethane) at a temperature between 0 ºC and 100 ºC. For related examples, see Liu, H. et al Bioorg. Med. Chem. (2008), 16, 10013, WO 2014/020350 and Kompella, A. et al Bioorg. Med. Chem. Lett. (2001), 1, 3161. The compounds of formula (VIII) are either commercially available or prepared using known methods. This reaction is shown in Scheme 6. Ri R day —— Bda HO x (VII) (VI) Scheme 6
[0088] [0088] Alternatively, the compounds of Formula (1) can be prepared from compounds of Formula (IX) by treatment with trifluoroacetic anhydride or trifluoroacetyl halide (including trifluoroacetyl fluoride, trifluoroacetyl chloride and trifluoroacetyl bromide) in the presence of a base (eg, pyridine or 4-dimethylaminopyridine) in a suitable solvent, (eg, ethyl acetate, tetrahydrofuran, 2-methyl-tetrahydrofuran, or ethanol), at a temperature between O ºC and 75 ºC. For related examples, see WO 2003/028729, WO 2017/118689, and WO 2010/045251. This reaction is shown in Scheme 7.
[0089] [0089] The compounds of Formula (IX), can be prepared from compounds of Formula (X) by treatment with a hydroxylamine hydrochloride salt or a solution of hydroxylamine in water, in the presence of a base, such as triethylamine or KXC03, in a suitable solvent, such as methanol or ethanol, at a temperature between 0 ºC and 100 ºC. In some cases, better reaction performance can be gained with the use of a catalyst (eg, 8-hydroxyquinoline). For related examples, see Kitamura, S. et al. Chem. Pharm. Bull. (2001), 49, 268 and WO 2013/066838. This reaction is shown in Scheme 8.
[0090] [0090] The compounds of Formula (X) can be prepared from compounds of Formula (XI), where Y is Cl, Br or I, by means of a reaction promoted by a metal with a suitable cyanide reagent, such as such as Pd (0) / Zn (CN)> or CuCN, in a suitable solvent (eg, dimethylformamide or N-methylpyrrolidone) at elevated temperature, between 80 ºC and 120 ºC. For related examples, see US 2007/0155739, WO 2017/118689, and WO 2009/022746. This reaction is shown in Scheme 9.
[0091] [0091] Compounds of Formula (XI), where Y is CN, Cl, Br, or LI, can be prepared from compounds of Formula (VII), where X is 0S0xCH3, Cl, Br, or I, through treatment with compounds of Formula (III), in the presence of a base (eg triethylamine, N, N-diisopropylethylamine, K2CO03, NaHCO3, Na2CO3, Cs2CO3, or NaH) in a suitable solvent (eg dimethylacetamide, tetrahydrofuran, 2-methyltetrahydrofuran, acetone, toluene, or acetonitrile) at a temperature between 25 ºC and 110 ºC. In some cases, a better reaction performance can be gained with the use of a catalyst (eg, BuaNHSOs, BUuaNBr, Bu4aNI, Nal, or 4-dimethylaminopyridine) and microwave irradiation. In addition, compounds of formula (XI) can optionally be obtained by coupling transformation with compounds of formula (III) and compounds of formula (VII), where X is OH, by means of a process that converts the - OOH in an improved leaving group, such as a -SO2CH3 group, for example using methanesulfonyl chloride (C1SO0XMe), before treatment with the compounds of formula (III). The compounds of formula (III) are either commercially available or prepared using known methods. For related examples, see WO 2013/132253, WO 2017/118689, and Garcia, M. et al Org. Biomol. Chem. (2004), 11, 1633. This reaction is shown in Scheme 10.
[0092] [0092] As already indicated, surprisingly, it has now been discovered that the compounds of Formula (I) of the present invention have, for practical purposes, a very advantageous level of biological activity for the protection of plants against diseases that are caused by fungi.
[0093] [0093] The compounds of Formula (I) can be used in the agricultural sector and related areas of use, eg as active ingredients to control plant pests or in non-living materials for the control of microorganisms that cause deterioration or organisms potentially harmful to man. The new compounds are distinguished by excellent activity at low application rates, by being well tolerated by plants and by being environmentally safe. They have very useful healing, preventive and systemic properties and can be used to protect various cultivated plants. The compounds of Formula (1) can be used to inhibit or destroy pests that occur in plants or parts of plants (fruit, flowers, leaves, stems, tubers, roots) from different crops of useful plants, while also protecting those parts of plants that grow later, for example, of phytopathogenic microorganisms.
[0094] [0094] The present invention additionally relates to a method to control or prevent infestation of plants or plant propagating material and / or harvested food crops susceptible to microbial attack, by treating plants or plant propagating material and / or harvested food crops, in which an effective amount of a compound of Formula (I) is applied to plants, parts of them or their location.
[0095] [0095] It is also possible to use compounds of Formula (1) as a fungicide. The term "fungicide", as used herein, means a compound that controls, modifies or prevents the growth of fungi. The term "fungicidal effective amount", when used, means the amount of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Control or modification effects include all deviations from natural development, such as death, retardation, and the like, and prevention includes a barrier or other defensive formation on or over a plant to prevent fungal infection.
[0096] [0096] It may also be possible to use compounds of Formula (1) as curative agents for the treatment of plant propagating material, eg seeds, such as fruits, tubers or grains, or plant cuttings, to protect against fungal infections, as well as against phytopathogenic fungi that occur in the soil. The propagation material can be treated with a composition comprising a compound of Formula (II) before planting: a seed, for example, can be treated before being sown. The active compounds of Formula (1) can also be applied to grains (coating), by impregnating the seeds in a liquid formulation or by coating them with a solid formulation. The composition can also be applied to the planting site when the propagation material is planted, for example, to the seedbed during sowing. The invention also relates to such methods of treating plant propagation material and to plant propagation material so treated.
[0097] [0097] Additionally, the compounds of Formula (1) can be used to control fungi in related areas, for example, in the protection of technical materials, including wood and technical products related to wood, in food storage, in hygiene management.
[0098] [0098] Additionally, the invention could be used to protect non-living materials from fungal attack, eg, construction wood, wall panels and paint.
[0099] [0099] The compounds of Formula (1) are, for example, effective against fungi and fungal disease vectors, as well as bacteria and phytopathogenic viruses. These fungi and fungal disease vectors, as well as phytopathogenic bacteria and viruses are, for example: Absidia corymbifera, Alternaria spp, Aphanomyces spp, Ascochyta spp, Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terrus, Aureobasidium spp. including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. including B. cinerea, Candida spp. including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis spp, Cercospora Spp. including C. arachidicola, Cercosporidium personatum, Cladosporium spp, Claviceps purpurea, Coccidioides immitis, Cochliobolus spp, Colletotrichum spp. including C. musae,
[0100] [0100] The compounds of Formula (1) can be used for example in peat, ornamental plants, such as flowers, shrubs, trees with broad or perennial leaves, for example conifers, as well as for tree injection, pest management and the like .
[0101] [0101] Within the scope of the present invention, target crops and / or useful plants to be protected typically comprise perennial and annual crops, such as berries, for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals, for example barley, maize (maize), millet, oats, rice, rye, sorghum, triticale and wheat; fiber plants, for example cotton, flax, hemp, jute and sisal; field crops, for example sugar beet and fodder, coffee, hops, mustard, rapeseed (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees, for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses, for example Bermuda grass, blue grass, agrostis, centipede grass, fescue, ryegrass, Saint Augustine grass and Zoysia grass; aromatic herbs such as basil, borage, chives, coriander, lavender, levistico, mint, oregano, parsley, rosemary, sage and thyme; legumes, for example beans, lentils, peas and soy; hard-shelled fruits, for example almond, cashew, peanut seed, hazelnut, peanut, pecan, pistachio and walnut; palms, for example palm oil; ornamental plants, for example flowers, shrubs and trees; other trees, for example cocoa, coconut, olive and rubber; vegetables, for example asparagus, eggplant, broccoli, cabbage, carrot, cucumber, garlic, lettuce, pumpkin, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomatoes; and vines, for example grapes.
[0102] [0102] The term "useful plants" should be understood to also include useful plants that have been made tolerant to herbicides such as bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfurone , prosulfurone and trifloxysulfurone, EPSPS (5-enol-pyrovyl-chiquimate-3-phosphate synthase) inhibitors, GS (glutamine synthase) inhibitors or PPO (protoporphyrinogen oxidase) inhibitors as a result of conventional methods of improvement or modification genetics. An example of a crop that has been made tolerant to imidazolinones, eg imazamox, by conventional breeding methods (mutagenesis) is the summer rape clearfieldo (Canola). Examples of crops that have been made tolerant to herbicides or classes of herbicides by genetic engineering methods include varieties of glyphosate and glufosinate resistant maize,
[0103] [0103] The term "useful plants" should be understood to also include useful plants that have been thus transformed by the use of recombinant DNA techniques in order to be able to synthesize one or more selectively acting toxins, as they are known, for example , from bacteria that produce toxins, especially those of the genus Bacillus.
[0104] [0104] Examples of such plants are: YieldGard (variety of maize that expresses a CryIA toxin (b)); YieldGard Rootworm (variety of maize that expresses a CryIIIB toxin (b1)); YieldGard Plus (more variety that expresses a CryIA toxin (b) and a CryIIIB toxin (bl1)); Starlink (more variety that expresses a Cry9 toxin (c)); Herculex I (variety of maize that expresses a CryIF toxin (a2) and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuUCOTN 33B (cotton variety that expresses a CryIA toxin (c)); Bollgard 1 (cotton variety that expresses a CryIA toxin (c)); Bollgard II (cotton variety that expresses a CryIA toxin (c) and a CryIIA toxin (b)); VIPCOT (cotton variety that expresses a VIP toxin); Newleaf (potato variety that expresses a CryIIIA toxin); NatureGard Agrisuree GT Advantage (glyphosate tolerance characteristic GA21), Agrisuree CB Advantage (corn borer (CB) Bt11 characteristic), Agrisureo RW (corn rootworm trait) and Protecta.
[0105] [0105] The term "cultures" should be understood to also include culture plants that have been so transformed by the use of recombinant DNA techniques in order to be able to synthesize one or more selectively acting toxins, as they are known, for example , of bacteria that produce toxins, especially those of the genus Bacillus.
[0106] [0106] Toxins that may be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or Bacillus thuringiensis insecticidal proteins, such as 6-endotoxins, eg, CrylAb, CrylAc, CrylF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins (Vip), eg, Vipl, Vip2, Vip3 or Vip3A; or insecticidal proteins from nematode-colonizing bacteria, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect specific neurotoxins; toxins produced by fungi, such as toxins from Streptomycetes, plant lectins, such as pea lectins, barley lectins or white bell lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome deactivating proteins (RIP), such as ricin, more RIP, abrina, lufina, saporina or briodina; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl transferase, cholesterol oxidases, ecdysone inhibitors,
[0107] [0107] Additionally, in the context of the present invention, S-endotoxins should be understood, for example, CrylAb, CrylAc, CrylF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins (Vip), for example, Vipl , Vip2, Vip3 or Vip3A, also expressly hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of these proteins (see, for example, WO 02/15701). Truncated oxines are known, for example a truncated Cryl1Ab. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid substitutions, protease recognition sequences not naturally present are preferably inserted into the toxin, such as, for example, in the case of Cry3A055, in which a cathepsin G recognition sequence is inserted into a Cry3A toxin (see WO 03 / 018810).
[0108] [0108] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP-AO 374 753, W093 / 07278, WO95 / 34656, EP-AO 427 529, EP-A-451 878 and WO 05/032073.
[0109] [0109] The processes for preparing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above. Deoxyribonucleic acids of the type
[0110] [0110] The toxin contained in transgenic plants gives plants tolerance to harmful insects. Such inserts can occur in any taxonomic group of insects, but they are especially commonly found in beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidopterans).
[0111] [0111] Transgenic plants are known to contain one or more genes that encode an insecticidal resistance and express one or more toxins, and some of them are commercially available. Examples of such plants are: YieldGard (variety of maize that expresses a Cryl1Ab toxin); YieldGard Rootworm (more variety that expresses a Cry3Bb1 toxin); YieldGard Plus (variety of apples that expresses a CrylAb toxin and a Cry3Bbl); Starlink (more variety that expresses a Cry9C toxin); Herculex I (variety of maize that expresses a CrylFa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NUCOTN 33B (cotton variety that expresses a Cryl1Ac toxin); Bollgard IT (cotton variety that expresses a CrylAc toxin); Bollgard IIG (cotton variety that expresses a CrylAc toxin and a Cry2Ab); VipCot (cotton variety that expresses a Vip3A toxin and a CrylAb); NewLeaf (potato variety that expresses a Cry3A toxin); NatureGard, Agrisuree GT Advantage (glyphosate tolerant feature GA21), Agrisuree CB Advantage (corn borer tolerant feature (CB) Btl11) and Protecta.
[0112] [0112] Additional examples of such transgenic crops are:
[0113] [0113] The compounds of Formula (1) (including any of the compounds 1.1 to 1.190) according to the present invention comprising a compound of Formula (1) can be used in the control or prevention of phytopathogenic diseases, especially phytopathogenic fungi ( such as Phakopsora pachyrhizi) in soybean plants.
[0114] [0114] In particular, soybean plants expressing toxins, for example insecticidal proteins such as delta-endotoxins, for example, CrylAc (Bt CrylAc protein). Consequently, this can include transgenic soybean plants comprising the MON87701 event (see U.S. Patent No. 8,049,071 and related applications and patents, as well as WO 2014/170327 A1 (see, e.g., paragraph
[008] [008] reference to Intacta RR2 PROM! ") Soybean, event MON87751 (US Patent Application Publication No. 2014/0373191) or DAS-81419 event (U.S. Patent No. 8,632978 and related applications and patents).
[0115] [0115] Other transgenic soybean plants may comprise the event SYHTOH2 - tolerance to HPPD (US Patent Application Publication No. 2014/0201860 and and related applications and patents), event MON89788 - tolerance to glyphosate (US Patent No. 7,632,985 and applications and patents event), event MON87708 - dicamba tolerance (US Patent Application Publication No. US 2011/0067134 and related applications and patents), event DP-356043-5 - glyphosate tolerance and ALS (US Patent Application Publication No. US 2010 / 0184079 and related patents and orders), event A2704-12 - glufosinate tolerance (US Patent Application Publication No. US 2008/0320616 and related patents and orders), event DP-305423-1 - ALS tolerance (Order Publication US Patent No. 2008/0312082 and related applications and patents), event A5547-127 - glufosinate tolerance (US Patent Application Publication No. US 2008/0196127 and related applications and patents), event DAS -40278-9 - tolerâ 2,4-dichlorophenoxyacetic acid and aryloxyphenoxypropionate (see WO 2011/022469, WO 2011/022470, WO 2011/022471, and related applications and patents), event 127 - ALS tolerance (WO 2010/080829 and applications and patents related events), event GTS 40-3-2 - glyphosate tolerance, event DAS-68416-4 -
[0116] [0116] Under certain circumstances, the compounds of Formula (1) according to the present invention when used in the control or prevention of phytopathogenic diseases, especially phytopathogenic fungi (such as Phakopsora pachyrhizi) in soybean plants (in particular any of the plants transgenic soybeans as described above), may have a synergistic interaction between the active ingredients.
[0117] [0117] The term “local”, as used herein, means fields in or on which plants grow, or where the seeds of cultivated plants are sown, or where the seed will be placed in the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
[0118] [0118] The term "plants" refers to all the physical parts of a plant, including seeds, seedlings, young plants, roots, tubers, stems, stems, foliage and fruits.
[0119] [0119] The term "plant propagating material" is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. For example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants can be mentioned. Germinated plants and young plants that must be transplanted after germination or after emergence from the soil, can also be mentioned. These young plants can be protected before transplantation through total or partial immersion treatment. Preferably, "plant propagation material" is understood to denote seeds.
[0120] [0120] The compounds of Formula (II) can be used in an unmodified form or, preferably, in conjunction with adjuvants conventionally employed in the formulation technique. For this purpose, they can be conveniently formulated in a known manner in emulsifiable concentrates, coated pastes, directly sprayable or dilutable solutions or suspensions, diluted emulsions, wettable powders, soluble powders, dust, granules and also encapsulations, e.g., in substances polymeric. As with the type of the compositions, the application methods, such as spraying, atomizing, dusty, dispersing, coating or spilling, are chosen according to the intended objectives and the prevailing circumstances. The compositions may also contain additional adjuvants such as stabilizers, defoamers, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
[0121] [0121] Suitable vehicles and adjuvants, eg for agricultural use, can be solid or liquid and are useful substances in formulation technology, eg, regenerated or natural mineral substances, solvents, dispersants, wetting agents, promoters stickiness, thickeners, binders or fertilizers. Such vehicles are described for example in WO 97/33890.
[0122] [0122] Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations include anti-settling agents and dispersing agents, and may additionally include a wetting agent to enhance the activity, as well as a defoamer and a crystal growth inhibitor. In use, these concentrates are diluted with water and usually applied as a spray to the area to be treated. The amount of active ingredient can vary from 0.5% to 95% of the concentrate.
[0123] [0123] Wettable powders are in the form of finely divided particles that readily disperse in water or other liquid vehicles. The particles contain the active ingredient retained in a solid matrix. Typical solid matrices include Fuller earth, kaolin clays, silica and other readily moistened organic or inorganic solids. Wettable powders usually contain 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.
[0124] [0124] Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and others non-volatile organic solvents. In use, these concentrates are dispersed in water or another liquid, and usually applied as a spray to the area to be treated. The amount of active ingredient can vary from 0.5% to 95% of the concentrate.
[0125] [0125] Granular formulations include both extruded and relatively coarse particles and are usually applied without dilution to the area where treatment is required. Typical vehicles for granular formulations include sand, Fuller earth, atapulgite clay, bentonite clay, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice stone, pyrophyllite, kaolin, dolomite, plaster, sawdust, cobs crushed corn, crushed peanut shells, sugars, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate and other organic or inorganic materials that absorb or can be coated with the active compound. Granular formulations normally contain 5% to 25% of active ingredients which may include surfactants, such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and / or adhesives, such as dextrins, glue or synthetic resins.
[0126] [0126] Powders are free-flowing mixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids that act as dispersants and vehicles.
[0127] [0127] Microcapsules are typically droplets or granules of the active ingredient contained in an inert porous shell that allows closed material to escape into the neighborhood at controlled rates. Encapsulated droplets are typically 1 to 50 microns in diameter. The enclosed liquid typically constitutes 50 to 95% of the weight of the capsule and can include a solvent in addition to the active compound. Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form within the granule pores. The granules typically range from 1 millimeter to 1 centimeter, and preferably from 1 to 2 millimeters in diameter. The granules are formed by extrusion, agglomeration or pelletizing, or they occur naturally. Examples of such materials are vermiculite, sintered clay, kaolin, atapulgite clay, sawdust and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthate.
[0128] [0128] Other formulations useful for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized sprayers, in which the active ingredient is dispersed in a finely divided form as a result of vaporizing a dispersing solvent vehicle with a low boiling point, can also be used.
[0129] [0129] Suitable agricultural adjuvants and vehicles that are useful in formulating the compositions of the invention in the types of formulations described above are well known to those skilled in the art.
[0130] [0130] Liquid vehicles that can be used include, for example, water, toluene, xylene, petroleum naphtha, vegetable oil, acetone, methyl ethyl ketone,
[0131] [0131] Suitable solid vehicles include, for example, talc, titanium dioxide, pyrophyllite clay, silica, atapulgite clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, Fuller earth, shells of cotton seeds, wheat flour, soy flour, pumice, sawdust, nutshell flour and lignin.
[0132] [0132] A wide variety of surfactants are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with vehicle before application. These agents, when used, normally comprise from 0.1% to 15% by weight of the formulation. They can be anionic, cationic, non-ionic or polymeric in character and can be used as emulsifying agents, wetting agents, suspending agents or for other purposes. Typical surfactants include salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub 18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl-ethoxylate alcohol C.sub. 16; Soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as di (2-ethylhexyl)
[0133] [0133] Other adjuvants commonly used in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, antifoaming agents, light blocking agents, compatibilizing agents, antifoaming agents , sequestering agents, neutralizing agents and buffers, corrosion inhibitors, dyes, flavorings, spreading agents, penetration aids, micronutrients, emollients, lubricants and adhesives.
[0134] [0134] Furthermore, in addition, other biocidal active ingredients or compositions can be combined with the compositions of the invention, used in the methods of the invention, and applied simultaneously or sequentially with the compositions of the invention. When applied simultaneously, these additional active ingredients can be formulated in conjunction with the compositions of the invention, or mixed, for example, in the spray tank. These biocidal active ingredients can be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and / or plant growth regulators.
[0135] [0135] Reference is made here to pesticide agents using their common name, known, for example, from “The Pesticide Manual”, 15th Edition, British Crop Protection Council 2009.
[0136] [0136] In addition, the compositions of the invention can also be applied with one or more inductors of systemically acquired resistance ("SAR" inductor). SAR inducers are known and described, for example, in United States Patent No. 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.
[0137] [0137] The compounds of Formula (1) are normally used in the form of agrochemical compositions, and can be applied to the crop area or plant to be treated, simultaneously or successively with other compounds. These additional compounds can be eg fertilizers or micronutrient donors or other preparations, which influence plant growth. They can also be selective herbicides or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired in conjunction with additional vehicles, surfactants or application-promoting adjuvants commonly employed in the formulation technique.
[0138] [0138] The compounds of Formula (1) can be used in the form of compositions (fungicides) to control or protect against phytopathogenic microorganisms, comprising as active ingredient at least one compound of Formula (I) or at least one preferred individual compound as herein defined, in free form or in the form of agro-chemically usable salt, and at least one of the aforementioned adjuvants.
[0139] [0139] The invention therefore provides a composition, preferably a fungicidal composition, comprising at least one compound of Formula (1), an agriculturally acceptable carrier and optionally an adjuvant. An acceptable agricultural vehicle is, for example, a vehicle that is suitable for agricultural use. Agricultural vehicles are well known in the art. Preferably, said composition may comprise at least one or more pesticide-active compounds, for example an additional fungicidal active ingredient in addition to the compound of Formula (1).
[0140] [0140] The compound of Formula (1) can be the only active ingredient in a composition or it can be mixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator, when appropriate. An additional active ingredient can, in some cases, result in unexpected synergistic activities.
[0141] [0141] Examples of suitable additional active ingredients include the following: acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenic fungicides, arylphenyl ketone fungicides, benzamide fungicides, benzanidide, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged diphenyl fungicides, carbamate fungicides, carbanylate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, fungicides, fungicides dithiolane, furamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine fungicides, oragnophosphorous fungicides, organo-tin fungicides, oxathin fungicides, oxazole fungicides, phenyl fungicides, fungicides pyre zol, pyridine fungicides, pyrimidine fungicides, pyrrole fungicides, quaternary ammonium fungicides, quinoline fungicides, quinone fungicides, quinoxaline fungicides, strobilurin fungicides, sulfonanilide fungicides, thiadiazole fungicides, thiadiazole fungicides, thia fungicides , thiocarbamate fungicides, thiophene fungicides, triazine fungicides, triazole fungicides, triazolopyrimidine fungicides, urea fungicides, valinamide fungicides and zinc fungicides.
[0142] [0142] Examples of suitable additional active ingredients also - include the following: —3-difluoromethyl-1-methyl-11H-pyrazolo-4-carboxylic acid (9-dichloromethylene-1,2,3,4-tetrahydro-1 , 4-methane-naphthalen-5-yl) -amide, methoxy- [1-methyl-2- (2,4,6-trichlorophenyl) -ethyl] -amide of 3-difluoromethyl-1-methyl-1H-pyrazole -4-carboxylic, (2-dichloromethylene-3-ethyl-1-methyl-indan-4-yl) - 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid amide (1072957-71-1) , 1-methyl-3-difluoromethyl-1H-pyrazolo-4-carboxylic acid (4'-methylsulfanyl-biphenyl-2-yl) -amide, [2- (2,4-dichloro-phenyl) -2-methoxy- 1-methyl-3-difluoromethyl-4H-pyrazole-4-carboxylic acid l-methyl-3-amide, (5-Chloro-2,4-dimethyl-pyridin-3-11) - (2,3,4 -
[0143] [0143] The compounds of the invention can also be used in combination with anthelmintic agents. Such anthelmintic agents include compounds selected from the class of macrocyclic lactone compounds such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin derivatives as described in EP-357460, EP-444964 e EP-594291. Additional anthelmintic agents include semi-synthetic and biosynthetic avermectin / milbemycin derivatives, such as those described in US-5015630, WO-9415944 and W0-9522552. Additional anthelmintic agents include benzimidazoles such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxybendazole, parbendazole and other members of the class. Additional anthelmintic agents include imidazothiazoles and tetrahydropyrimidines, such as tetramisole, levamisole, pyrantel pamoate, oxantel or morantel. Additional anthelmintic agents include fluquicides, such as triclabendazole and clorsulon, and cestocides, such as praziquantel and epsiprantel.
[0144] [0144] The compounds of the invention can be used in combination with derivatives and analogs of the anthelmintic agent class of paraherquamides / marcfortins, as well as with antiparasitic oxazolines such as those disclosed in US-5478855, US4639771 and DE-19520936 .
[0145] [0145] The compounds of the invention can be used in combination with derivatives and analogs of the general class of agents - “dioxomorpholine antiparasitic agents as described in WO 96/15121 and also with active anthelmintic cyclic depsipeptides such as those described in WO 96 / 11945, WO 93/19053, WO 93/25543, EP O 626 375, EP O 382 173, WO 94/19334, EP O 382 173 and EP O 503 538.
[0146] [0146] The compounds of the invention can be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenurone; ecdysone agonists such as tebufenozide and similar neonicotinoids such as imidacloprid and the like.
[0147] [0147] The compounds of the invention can be used in combination with terpene alkaloids, for example those described in International Patent Application Publications Numbers WO 95/19363 or WO 04/72086, particularly with the compounds disclosed therein.
[0148] [0148] Other examples of such biologically active compounds with which the compounds of the invention can be used in combination include, but are not limited to, the following: Organophosphates: Aphosphate, Azametiphos, Azymphos-Ethyl, Azymphos-Methyl, Bromophos, Bromophos-Ethyl , cadusafós, chloretoxifós, chloropyrifós, chlorofenvinfós, chloromefós, demetone, demetona-S-methyl, demetone-S-methylsulfone, dialiphos diazinone, dichlorvós, dichrotophos, dimethoate, disulfotone, etione, etoprofós, féninfos, féninfos, fenetros, , flupirazofós, fonofós, Tformotiona, fostiazato, heptenofós, isazofós, isothioato, isoxathione, malationa, metacrifós, metamidofós, metidathione, methyl-parathione, mevinfós, monocrotofós, nalede, metetoate, paraoxoxone
[0149] [0149] Carbamates: alanicarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloetocarb, etiofencarb, phenoxycarb, fentiocarb, methacrocarb, methoxy, 5, isocarocarb, isoprocarb, 5 -m- cumenylbutyryl (methyl) carbamate, oxamyl, pyrimicarb, propoxur, thiodicarb, thiophanox, triazamate, UC-51717.
[0150] [0150] Pyrethroids: acrinatin, alethrin, alfamethrin, (E) - (1R) -cis-2,2-dimethyl-3- (2-oxothiolan-3-ylidenomethyl) 5-benzyl-3-furylmethyl, bifenthrin, cyclopropanecarboxylate beta-cyfluthrin, cyfluthrin, o-cypermethrin, beta-cypermethrin, bioalethrin, bioalethrin (isomer (S) -cyclopentyl), bioresmethrin, bifenthrin, NCI- 85193, cycloprotrin, cyhalothrin, cyttrin, cyphenothrin, emtenthetrin, emptametrine, deltametrine, deltametrine, delta fenflutrin, fenpropatrin, fenvalerate, flucitrinate, flumethrin, fluvalinate (D-isomer), imiprothrin, cyhalothrin, lambda-cyhalothrin, permethrin, phenothrin, pralethrin, pyrethrins (natural products), resmethrin, tetramethrin, transflutrin, tetrahydrin, tetrahydrin, tetrahydrin, tetrahydrin, fluvalinate, teflutrin, tralometrine, zeta-cypermethrin.
[0151] [0151] Arthropod growth regulators: a) chitin synthesis inhibitors: benzoylureas:
[0152] [0152] Other antiparasitic agents: acequinocila, amitraz, AKD-1022, ANS-118, azadiractin, Bacillus turingiensis, bensultape, biphenazate, binapacryl, bromopropylate, BTG-504, BTG-505, canfeclor, cartape, chlorodenzema, chlorodiene , clothianidin, cyromazine, diaclodene, diafentiurone, DBI-3204, dinactin, di-hdroxymethyldihydroxypyrrolidine, dinobutone, dinocape, endosulfan, etiprol, etofenprox, phenazaquin, flumite, MTI- 800, fliroxin, fluoroxime, fluorimine , fluproxifene, halofenprox, hydramethylnone, IKI-220, canemite, NC-196, neem protector, nidinorterfuran, nitanpirame, SD-35651, WL-108477, pyridine, propargite, protrifenbute, pimetrozine, pyridine, pyridine, pyridine, pyridine, pyridine, pyrimide -195, RH-0345, RH-2485, RYI-210, S $ -1283, Ss-1833, SI-8601, silafluofen, silomadin, spinosade, tebufenpirade, tetradifone, tetranactin, thiaclopride, thiocyame, thiamethoxam, tolfenpirade, triazamate triethoxyspinosine, tr inactin, verbutin, vertalec, YI-5301.
[0153] [0153] Biological agents: Bacillus thuringiensis sSp aizawai, kurstaki, detla Bacillus thuringiensis endotoxin, baculovirus, entomopathogenic bacteria, viruses and fungi.
[0154] [0154] Bactericides: chlortetracycline, oxytetracycline, streptomycin.
[0155] [0155] Other biological agents: enrofloxacin, febantel, penetamate, moloxicame, cephalexin, kanamycin, pimobendan, clenbuterol, omeprazole, tiamulin, benazepril, pyriprol, cefquinoma, florfenicol, buserelin, cefoviprine, trefohydrate, cefovecin, trefovinine, trefovinine, cefovecin, trefovinine, cefovantine, trefoiline, .
[0156] [0156] The following mixtures of the compounds of Formula (1) with active ingredients are preferred. The abbreviation “TX” means a compound selected from the group consisting of compounds as shown in Tables 1.1 to 1.3 and Tables 2.1 to 2.2 (below), or compounds 1.1 to 1,190 described in Table T1 (below): an adjuvant selected from the group of substances consisting of petroleum-derived oils (alternative name) (628) + TX, an acaricide selected from the group of substances consisting of 1,1-bis (4-chlorophenyl) -2-ethoxyethanol (IUPAC name) (910) + TX , 2,4-dichlorophenyl benzenesulfonate (IUPAC / Chemical Abstracts name) (1059) + TX, 2-fluoro-N-methyl-N1-naphthylacetamide (IUPAC name) (1295) + TX, 4-chlorophenylphenylsulfone (IUPAC name) (981) + TX, abamectin (1) + TX, acequinocyl (3) + TX, acetoprol [CCN] + TX, acrinatrin (9) + TX, aldicarb (16) + TX, aldoxicarb (863) + TX, alpha- cypermethrin (202) + TX, amidithione (870) + TX, amidoflumete [CCN] + TX, amidothioate (872) + TX, amitone (875) + TX, amitone hydrogen oxalate (875) + TX, amitraz
[0157] [0157] or a biologically active compound selected from the group consisting of N - [(5-chloro-2-isopropyl-phenyl) methyl] - N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-pyrazole- 4-carboxamide (can be prepared according to the procedures described in WO 2010/130767) + TX, 2,6-dimethyl-1H, 5H- [1,4] dithiine [2,3-c: 5.6 -c '] dipyrrol- 1,3,5,7 (2H, 6H) -tetrone (can be prepared according to the procedures described in WO 2011/138281) + TX, 6-ethyl-5,7-dioxo-pyrrole [4,5] [1,4] dithino [1,2-c] isothiazole-3-carbonitrile + TX, 4- (2-bromo-4-fluoro-phenyl) -N- (2-chloro-6 - fluoro-phenyl) -2,5-dimethyl-pyrazol-3-amine (can be prepared according to the procedures described in WO 2012/031061) + TX, 3- (difluoromethyl) -N- (7-fluoro-1 , 1,3-trimethyl-indan-4-1yl) -1-methyl-pyrazol-4-carboxamide (can be prepared according to the procedures described in WO 2012/084812) + TX, CAS 850881-30-0 + TX , 3- (3,4-dichloro-1,2-thiazol-5-ylmethoxy) -1,2-benzothiazole 1,1-dioxide (can be prepared according to the procedures described in document 7) 2007/129454) + TX, 2- [2 - [(2,5-dimethylphenoxy) methyl] phenyl] -2-methoxy-N-methyl-acetamide + TX, 3- (4.4 -difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl) quinolone (can be prepared according to the procedures described in WO 2005/070917) + TX, 2- [2-
[0158] [0158] References in parentheses before the active ingredients, eg [3878-19-1] refer to the Chemical Abstracts Registration Number. The mixing partners described above are known. When the active ingredients are included in “The Pesticide Manual” [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council], they are described there under the entry number given in curly brackets above in this document for the particular compound; for example, the compound "abamectin" is described under the entry number (1). When "[CCN]" is added above in this document to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which can be accessed over the internet [A. Wood; Compendium of Pesticide Common Names, Copyright O &1995-2004]; for example, the compound "acetoprol" is described at http: // www. alanwood.net/pesticides/acetoprole.html.
[0159] [0159] Most of the active ingredients described above are referred to previously by a so-called “common name”, with the relevant “common name ISO” or another “common name” used in individual cases. If the designation is not a “common name”, the nature of the designation used instead is given in curly brackets for the particular compound; in that case the name IUPAC, the name IUPAC / Chemical Abstracts, a “chemical name”, a “traditional name”, a “compound name” or a “development code” are used or, if neither of these designations is used nor a “common name”, an “alternative name” is used. “CAS Registry No.” means the Chemical Abstracts Registration Number.
[0160] [0160] The mixture of active ingredients of the compounds of formula (1) selected from a compound as represented in Tables 1.1 to 1.3 and Tables 2.1 and 2.2 (below), or from compounds 1.1 to 1,190 described in Table T1 (below), it is preferably in a mixing ratio of 100: 1 to 1: 6000, especially from 50: 1 to 1:50, more especially in a ratio of 20: 1 to 1:20, even more especially from 10: 1 to 1: 10, most notably 5: 1 and 1: 5, with a particular preference being given to a ratio of 2: 1 to 1: 2, and a ratio of 4: 1 to 2: 1 being equally preferred, above all in a ratio of 1: 1, or 5: 1, or 5: 2, or 5: 3, or 5: 4, or 4: 1, or 4: 2, or 4: 3, or 3: 1, or 3: 2, or 2: 1, or 1: 5, or 2: 5, or 3: 5, or 4: 5, or 1: 4, or 2: 4, or 3: 4, or 1: 3, or 2: 3, or 1: 2, or 1: 600, or 1: 300, or 1: 150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1: 6000, or 1: 3000, or 1: 1500, or 1: 350, or 2: 350, or 4: 350, or 1: 750, or 2: 750, or 4: 750. These mixing ratios are by weight.
[0161] [0161] Mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to pests or their environment, with the exception of a method for treating the body human or animal by surgery or therapy and diagnostic methods practiced on the human or animal body.
[0162] [0162] Mixtures comprising a compound as shown in Tables 1.1 to 1.3 and Tables 2.1 and 2.2 (below), or compounds 1.1 to 1,190 described in Table T1 (below), and one or more active ingredients as described above can be applied, for example, in a single “ready-mix” form in a combined spray mixture composed of separate formulations of the components of unique active ingredients, such as in the “tank mix”, and in a combined use of the unique active ingredients when applied sequentially, that is, one after the other with a relatively short period, such as a few hours or days. The order of application of a compound as represented in Tables 1.1 to 1.3 and Tables 2.1 and
[0163] [0163] The compositions according to the invention may also - comprise additional solid or liquid auxiliaries, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example coconut oil, rapeseed oil or epoxidized soybean oil), defoamers , for example silicone oil, preservatives, viscosity regulators, binders and / or adhesives, fertilizers or other active ingredients to achieve specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
[0164] [0164] The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries, for example by grinding, sieving and / or compression of a solid active ingredient and in the presence of at least one auxiliary, for example by intimate mixing and / or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of compounds (TI) for the preparation of these compositions are also a subject of the invention.
[0165] [0165] Another aspect of the invention relates to the use of a compound of Formula (TI) or a preferred individual compound as defined herein, a composition comprising at least one compound of Formula (1) or at least one individual compound preferred as defined above, or a fungicidal or insecticidal mixture comprising at least one compound of Formula (I) or at least one preferred individual compound as defined above, in admixture with other fungicides or insecticides as described above, to control or prevent infestation of plants, eg useful plants, such as crop plants, their propagating material, eg seeds, harvested crops, eg harvested food crops, or non-living materials by insects or microorganisms phytopathogenic, preferably fungal organisms.
[0166] [0166] A further aspect of the invention relates to a method for controlling or preventing an infestation of plants, eg, useful plants such as crop plants, plant propagating material, eg seeds, harvested crops, eg food crops harvested, or from non-living materials by insects or phytopathogenic or deteriorating microorganisms or organisms potentially harmful to humans, especially fungal organisms, which comprises the application of a compound of Formula (1) or a compound preferred individual as defined above as an active ingredient for plants, parts of plants or their location, propagating material for them, or any part of non-living materials.
[0167] [0167] Means of control or prevention that reduce infestation by phytopathogenic or deteriorating microorganisms or organisms that are potentially harmful to humans, especially fungal organisms, to such an extent that an improvement is demonstrated.
[0168] [0168] A preferred method of controlling or preventing an infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, or insects, which comprises the application of a compound of Formula (1), or an agrochemical composition containing at least one of these compounds, is the foliar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen or insect. However, the compounds of Formula (1) can also penetrate the plant through the roots through the soil (systemic action) by soaking the plant site with a liquid Formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (application to soil). In irrigated rice crops, such granules can be applied to the irrigated rice field. The compounds of Formula (1) can also be applied to seeds (coating) by impregnating the seeds or tubers with a liquid formulation of the fungicide or by coating them with a solid formulation.
[0169] [0169] A formulation, e.g. a composition containing the compound of Formula (I) and, if desired, a solid or liquid adjuvant or monomers for encapsulating the compound of Formula (1), can be prepared in a known manner , typically by intimate mixing and / or grinding the compound with diluents, for example solvents, solid vehicles and, optionally, surfactant compounds.
[0170] [0170] Advantageous application rates usually range from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 109 to 1Kk9 a.i./ha, more preferably from 20g to 600g a.i./ha. When used as a seed drenching agent, convenient dosages range from 10 mg to 1 g of active substance per kg of seeds.
[0171] [0171] When the combinations of the present invention are used to treat seeds, rates of 0.001 to 50 g of a compound of Formula (1) per kg of seed, preferably from 0.01 to 109 per kg of seed are generally sufficient.
[0172] [0172] Suitably, a composition comprising a compound of Formula (I) according to the present invention is applied preventively, which means before the development of the disease, or dressing, which means after the development of the disease.
[0173] [0173] The compositions of the invention can be used in any conventional form, for example, in the form of a double pack, a powder for the dry treatment of seeds (DS), an emulsion for the treatment of seeds (ES), a concentrate capable of flowing for seed treatment
[0174] [0174] Such compositions can be produced in a conventional manner, eg by mixing the active ingredients with appropriate inert formulation agents (diluents, solvents, fillers and optionally other formulation ingredients such as surfactants, biocides, antifreeze, adhesives, thickeners and compounds that provide adjuvant effects). Conventional slow release formulations can also be employed when long-term efficacy is desired. In particular, formulations to be applied to spray forms, such as water-dispersible concentrates (eg EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as as wetting and dispersing agents, and other compounds that provide adjuvant effects, e.g.
[0175] [0175] A seed treatment formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in the form of a suitable seed treatment formulation, eg as an aqueous suspension or in a form of dry powder with good adhesion to seeds. Such seed treatment formulations are known in the art. Seed treatment formulations can contain the single active ingredients or the combination of active ingredients in encapsulated form, eg, as slow-release capsules or microcapsules.
[0176] [0176] In general, formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% of agriculturally acceptable surfactant, and 10 to 99.99% of solid or liquid inert formulation agents and adjuvant ( s), the active agent consisting of at least the compound of Formula (I) optionally in conjunction with other active agents, particularly microbiocides or preservatives or the like. Concentrated forms of compositions generally contain between about 2 and 80%, preferably between about 5 and 70% by weight of active agent. Forms of application of the formulation may contain, for example, from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Although commercial products are preferably formulated as concentrates, the end user will normally employ diluted formulations.
[0177] [0177] Although it is preferable to formulate commercial products as concentrates, the end user will normally use diluted formulations.
[0178] [0178] Table 1.1: This table discloses 65 specific compounds of formula (T-1): 1 R N. da = F
[0179] [0179] Each of Tables 1.2 to 1.3 (which follow Table
[0180] [0180] Table 1.2: This table discloses 65 specific compounds of formula (T-1), where A is 3,5-thienyl and RL and Rº are hydrogen, Z is as defined above in Table 1.
[0181] [0181] Table 1.3: This table discloses 65 specific compounds of formula (T-1), where A is 2,5-thienyl and Rº is hydrogen, Rº is methyl, and Z is as defined above in Table 1.
[0182] [0182] Table 2.1: This table discloses 372 specific compounds of formula (T-2): 1 R ny F E Ss N / NO (T-2) where R! is hydrogen and Z is as defined below in Table 2.
[0183] [0183] Table 2.2 (following Table 2.1) makes 372 individual compounds of formula (T-2) available in which R! it is as specifically defined in Table 2.2, which refers to Table 2, where Z is specifically defined. Table 2 Compound Compound
[0184] [0184] Table 2.2: This table discloses 372 specific compounds of formula (T-2), where R! is methyl and Z is as defined above in Table 2.
[0185] [0185] For Z as defined in Tables 1 and 2 above (with the exceptions of compounds No. 1,034, 1,036 to 1,039, 1,041 to 1,043, 1,046 to 1,048, 1,050, 1,051, 1,053 to 1,065 identified as radicals), groups are disclosed Z as a compound where the nitrogen in the available ring (as designated by an NH group) is the point of attachment to the rest of the molecule according to a Z radical for the compounds of Formula (1) of the present invention.
[0186] [0186] As an example, the radical Z of compound 1.001 (1H-pyrazole-4-carboxylic acid) in Table 1 is: T
[0187] [0187] The following general procedure was used in a combinatorial manner using appropriate building blocks (compounds of Formulas (II) and (III)) to provide the compounds of Formula (TI). The compounds prepared using the following combinatorial protocol were analyzed using LC / NMS Method B. EXAMPLES
[0188] [0188] The following Examples serve to illustrate the invention. The compounds of the invention can be distinguished from known compounds by virtue of their greater effectiveness at low rates of application, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower rates of application if necessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.
[0189] [0189] The compounds of Formula (1) can have any number of benefits including, but not limited to, advantageous levels of biological activity to protect plants against diseases that are caused by fungi, or superior properties for use as active agrochemical ingredients (for example, increased biological activity, an advantageous spectrum of activity, an increased safety profile (including improved crop tolerance), improved physico-chemical properties or increased biodegradability).
[0190] [0190] Throughout this description, temperatures are presented in degrees Celsius (ºC) and "p.f." means melting point. LC / MS stands for Liquid Chromatography - Mass Spectroscopy and the description of the apparatus and method (Methods A, B and C) is as follows: The description of the LC / MS apparatus and method A is: SQ 2 detector of Waters Ionization method: Electrospray Polarity: positive and negative ions Capillary (kV) 3.0, Cone (V) 30.00, Extractor (V) 2.00, Source temperature (ºC) 150, Desolvation temperature (ºC) 350, Cone Gas Flow (L / Hr) O, Desolvation Gas Flow (L / Hr) 650 Mass range: 100 to 900 DAD wavelength range (nm): 210 to 500 UPLC ACQUITY method from Waters with the following HPLC gradient conditions: (Solvent A: Water / Methanol 20: 1 + 0.05% formic acid and Solvent B: Acetonitrile + 0.05% formic acid)
[0191] [0191] The description of the LC / MS device and method B is: Waters SQ 2 detector Ionization method: Electrospray Polarity: positive ions Capillary (kV) 3.5, Cone (V) 30.00, Extractor (V ) 3.00, Source Temperature (ºC) 150, Desolvation Temperature (ºC) 400, Cone Gas Flow (L / Hr) 60, Desolvation Gas Flow (L / Hr) 700 Mass range: 140 to 800 DAD (nm) wavelength range: 210 to 400 Waters UPLC ACQUITY method with the following HPLC gradient conditions: (Solvent A: Water / Methanol 9: 1 + 0.1% formic acid and Solvent B: Acetonitrile + formic acid at 0.1%) Time (minutes) A (%) B (*%) Flow rate (mL / min) o 100 o 0.75 2.5 o 100 0.75 2.8 o 100 0.75 3.0 100 or 0.75
[0192] [0192] Column type: Waters ACQUITY UPLC HSS T3 Column length: 30 mm; Column internal diameter: 2.1 mm; Particle Size: 1.8 microns; Temperature: 60 ºC.
[0193] [0193] The description of the LC / MS apparatus and method C is: Waters SQ 2 detector Ionization method: Electrospray ACQUITY H Class UPLC, Waters Mass Spectrometer Polarity: Positive and Negative Polarity Switch Scanner type MS1 Scan Capillary (kV) 3.00, Cone (V) 40.00, Desolvation Temperature (ºC) 500, Gas Flow in the Cone (L / Hr) 50, Desolvation Gas Flow (L / Hr) 1000 Mass range : O to 2000 DAD wavelength range (nm): 200 to 350 Waters UPLC ACQUITY method with the following HPLC gradient conditions: (Solvent A: Water + 0.1% formic acid and Solvent B: Acetonitrile) Time (minutes) A (%) B (*%) Flow rate (mL / min) o 70 30 0.5 0.05 70 30 0.5 0.8 5 95 0.5 1.8 5 95 0, 5 2.45 70 30 0.5 2.50 70 30 0.5
[0194] [0194] Column type: Waters ACQUITY UPLC BEH C18; Column length: 50 mm; Column internal diameter: 2.1 mm; Particle Size: 1.7 microns; Temperature: 35 ºC.
[0195] [0195] When necessary, the enantiomerically pure final compounds can be obtained from racemic materials as appropriate, using standard physical separation techniques such as reverse phase chiral chromatography, or through stereoselective synthetic techniques, e.g. using chiral starting materials.
[0196] [0196] The active ingredient is carefully mixed with the adjuvants and the mixture is carefully ground in a suitable mill, giving rise to wettable powders that can be diluted with water to give suspensions of the desired concentration.
[0197] [0197] The active ingredient is carefully mixed with the adjuvants and the mixture is carefully ground in a suitable mill, creating powders that can be used directly for seed treatment.
[0198] [0198] Emulsions of any required dilution, which can be used to protect plants, can be obtained from this concentrate by dilution with water.
[0199] [0199] Ready-to-use powders are obtained by mixing the active ingredient with the vehicle and crushing the mixture in a suitable mill. Such powders can also be used for dry seed coatings.
[0200] [0200] The active ingredient is mixed and crushed with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in an air stream.
[0201] [0201] The finely crushed active ingredient is uniformly applied, in a mixer, to kaolin moistened with polyethylene glycol. The non-dusty coated granules are obtained in this way. Suspension concentrate Active ingredient [compound of Formula (1)] 40% Propylene glycol 10% Polyethylene glycol nonylphenolic ether (15 mol 6% ethylene oxide) Sodium lignosulfonate 10% Carboxymethylcellulose 1% Silicone oil (in the form of an emulsion a 75 1%% in water) Water 32%
[0202] [0202] The finely ground active ingredient is intimately mixed with the adjuvants, giving rise to a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, live plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, spilling or immersion. Flowable concentrate for seed treatment Active ingredient [compound of Formula (1)] 40% propylene glycol 5% butanol PO / EO copolymer 2% tristyrenophenol with 10-20 moles of EO 2% 1,2-benzisothiazolin-3-one ( in the form of a 0.5% 20% solution in water) 5% pigment monoazo calcium salt Silicone oil (in the form of a 0.2% emulsion 75% in water) Water 45.3%
[0203] [0203] The finely ground active ingredient is intimately mixed with the adjuvants, giving rise to a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, live plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, spilling or immersion. Suspension of slow-release capsules
[0204] [0204] 28 parts of a combination of the compound of Formula (1) are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate / polymethylene-polyphenylisocyanate mixture (8: 1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is reached. To this emulsion, a mixture of 2.8 parts of
[0205] [0205] The suspension of capsules obtained is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The Capsule Suspension Formulation contains 28% of the active ingredients. The average capsule diameter is 8-15 microns.
[0206] [0206] The resulting formulation is applied to the seeds as an aqueous suspension in an apparatus suitable for this purpose. AIBN = azobisisobutyronitrile DMF = dimethylformamide DMA = dimethylacetamide DIPEA = N, N-diisopropylethylamine EtOAc = ethyl acetate HCl = hydrochloric acid mp = melting point ºC = degrees Celsius MeOH = methyl alcohol Nao0H = sodium hydroxide NBS = N-hydroxide min = minutes ok = room temperature h = hour (s) TFAA = trifluoroacetic acid anhydride THF = tetrahydrofuran Tr = retention time (in minutes) LC / MS = Liquid Chromatography - Mass Spectrometry (description of the apparatus and methods used for the LC / MS analysis is given above)
[0207] [0207] Using the synthetic techniques described both above and below, the compounds of formula (I) can be prepared accordingly.
[0208] [0208] Example 1: This example illustrates the preparation of N, N-dimethyl-1 - [[5- [5- (trifluoromethyl) -1,2,4-0xadiazol-3-yl] -2-thienyl] methyl] -1,2,4-triazole-3-amine (Compound 1.4 of Table 71). men = No DSI A
[0209] [0209] To a suspension of 5-meylthiophene-2-carbonitrile (9.0 g, 73 mmol) in ethanol (365 mL) while stirring at room temperature was added triethylamine (20.6 mL, 146 mmol) followed by introduction into portions of hydroxylamine hydrochloride (10.3 g, 146 mmol). The reaction content was heated to reflux for 3.5 hours, cooled to 25 ° C, and concentrated under reduced pressure to provide N'-hydroxy-5-methyl-thiophene-2-carboxamidine as an impure residue which was used in the following transformations without further purification. LC / MS (Method A) retention time = 0.24 minutes, 156 (M + H).
[0210] [0210] In a suspension of impure N'-hydroxy-5-methyl-thiophene-2-carboxamidine (32.0 g) in tetrahydrofuran (1.0 L), pyridine (24 mL, 292 mmol) was introduced and the content was cooled to 10 ºC. TFAA (30.9 mL, 219 mL) was introduced into this suspension. The reaction mixture was allowed to warm to 25 ° C overnight, and then concentrated under reduced pressure. The resulting residue was dissolved in ethyl acetate, washed with a 1M aqueous solution of HCl, water, and a saturated aqueous solution of NazCO3. The organic layer was dried over sodium sulfate, filtered, and the volatiles were removed under reduced pressure. The impure residue was purified by flash chromatography with silica gel using a cyclohexane / EtO0Ac 'eluent gradient to give 3- (5-methyl-2-thienyl) -5- (trifluoromethyl) -1,2, 4-0xadiazole as a clear oil (13.1 g, 76% yield). LC / MS (Method A) retention time = 1.13 minutes, mass not detected.
[0211] [0211] 1H NMR (400 MHz, CDCl3) 5 ppm: 7.68 (d, 1H), 6.84 (d, 1H), 2.57 (s, 3H).
[0212] [0212] 19F NMR (400 MHz, CDCl3) 5 ppm: -65.44 (s). Step 3a: Preparation of 3- [5- (bromomethyl) -2-thienyl] -5- (trifluoromethyl) -1,2,4-0xadiazole
[0213] [0213] To a solution of 3- (5-methyl-2-thienyl) -5- (trifluoromethyl) -1,2,4-0xadiazole (13.1 g, 55.7 mmol) and tetrachloromethane (111 mL) under argon atmosphere was added AIBN (0.93 g, 5.6 mmol) and then NBS (11.02 g, 61.3 mmol). The contents were heated to 70 ° C for 18 hours. The mixture was cooled to 25 ºC and then diluted with dichloromethane and water. The layers were separated, the organic phase was dried over sodium sulfate, and the volatiles were removed under reduced pressure. The impure residue was purified by flash chromatography with silica gel using a cyclohexane / EtOAc eluent gradient to give 3- [5- (bromomethyl) -2-thienyl] -5- (trifluoromethyl) -1,2 , 4-0xadiazole as a yellow oil (3.86 g, 22% yield). LC / MS (Method A) retention time = 1.14 minutes, mass not detected.
[0214] [0214] 1H NMR (400 MHz, CDCl3) 5 ppm: 8.11 (d, 1H), 7.55 (d, 1H), 4.53 (s, 2H).
[0215] [0215] 19F NMR (400 MHz, CDCl3) 5 ppm: -65.31 (s).
[0216] [0216] 3- [5- (dibromomethyl) -2-thienyl] -5- (trifluoromethyl) -1,2,4-o0xadiazole was isolated as a by-product as a yellow amorphous solid (13.0 9g) Ss N
[0217] [0217] A solution of 3- [5- (bromomethyl) -2-thienyl] -5- (trifluoromethyl) -1,2,4-0xadiazole (150 mg, 0.48 mmol), N, N-dimethyl-4H -1,2,4-triazole-3-amine (64 mg, 0.57 mmol), and potassium carbonate (133 mg, 0.96 mmol) in acetonitrile (6.0 mL) was stirred at rt overnight . The solids were removed by filtration, washed with ethyl acetate, and the volatiles were removed under reduced pressure. The resulting residue was purified by flash chromatography with silica gel using a cyclohexane / Et0Ac 'eluent gradient to give N, N-dimethyl-1 - [[5- [5- (trifluoromethyl) -1,2 , 4-0xadiazol-3-yl] -2-thienyl] methyl] - 1,2,4-triazole-3-amine as a yellow solid (49 mg, 30% yield). LC / MS (Method A) retention time = 0.96 minutes, 345 (M + H). m.p .: 113-116 ºC.
[0218] [0218] 1H NMR (400 MHz, CDCl3) 5 ppm: 7.78 (s, 1H), 7.75 (d, 1H), 7.11 (d, 1H), 5.37 (s, 2H), 2.99 (s, 6H).
[0219] [0219] Example 2: This example illustrates the preparation of 1- [[5- [5- (trifluoromethyl) -1,2,4-0xadiazol-3-yl] -2-thienyl] methyl] -1,2,4 methyl methyl triazole-3-carboxylate (Compound 1.6 from Table T1).
[0220] [0220] A mixture of 3- [5- (bromomethyl) -2-thienyl] -5- (trifluoromethyl) -1,2,4-0xadiazole (1.0 g, 3.2 mmol), 1H-1.2 , Methyl 4-triazolo-3-carboxylate (610 mg, 4.8 mmol) and potassium carbonate (880 mg, 6.4 mmol) in acetonitrile (32 mL) was heated at 110 ° C for 2 hours. The resulting orange suspension was filtered to remove the solids and the filtrate solution was then concentrated under reduced pressure. The resulting impure residue was purified by chromatography on silica gel using a cyclohexane / ethyl acetate gradient to give 750 mg of the title compound as a white solid. LC / MS (Method A) retention time = 0.91 minutes, 360 (M + H).
[0221] [0221] 1H NMR (400 MHz, CDCl3) 5 ppm: 8.25 (s, 1H), 7.81 (d, 1H), 7.22 (d, 1H), 5.65 (s, 2H), 4.05 (s, 3H).
[0222] [0222] o 2 - [[5- [5- (trifluoromethyl) -1,2,4-0xadiazol-3-yl] -2-thienyl] methyl] -1,2,4-triazolo-3-carboxylate (Compound 1.55 from Table T1) was isolated as a by-product in the form of a colorless gum (306 mg), LC / MS (Method A) retention time = 0.91 minutes, 360 (M + H). The :
[0223] [0223] 1H NMR (400 MHz, CDCl3) 5 ppm: 8.05 (s, 1H), 7.75 (d, 1H), 7.22 (d, 1H), 6.50 (s, 2H), 4.05 (s, 3H).
[0224] [0224] Example 3: This example illustrates the preparation of 2- [[5- [5- (trifluoromethyl) -1,2,4-0xadiazol-3-yl] -2-thienyl] methyl] -1,2,4 propyl triazole-3-carboxylate (Compound 1.44 from Table 711). H3ECÓA IS NU: WE Ss N = DA and No
[0225] [0225] In a solution of 2 - [[5- [5- (trifluoromethyl) -1,2,4-oxadiazol-3-yl] -2-thienyl] methyl] -1,2,4-triazole-3- methyl carboxylate (100 mg, 0.27 mmol) and propanol (0.83 ml) concentrated sulfuric acid (0.01 ml) was introduced. The white suspension was stirred for 12 hours under reflux, during which time it became a clear solution. The resulting reaction mixture was concentrated under reduced pressure and the residue was purified by flash chromatography on silica gel using a cyclohexane / ethyl acetate gradient to give 47mg of the title compound as a colorless gum. LC / MS (Method A) retention time = 1.10 minutes, 388 (M + H).
[0226] [0226] 1H NMR (400 MHz, CDCl3) 5 ppm: 8.05 (s, 1H), 7.75 (d, 1H), 7.25 (d, 1H), 6.05 (s, 2H), 4.45 (t, 2H), 1.85 (m, 2H), 1.05 (t, 3H)
[0227] [0227] Example 4: This example illustrates the preparation of N-methyl-N-methoxy-2 - [[5- [5- (trifluoromethyl) -1,2,4-0xadiazol-3-yl] -2-thienyl] methyl] -1,2,4-triazolo-3-carboxamide (Compound
[0228] [0228] In a clear solution of O-methylhydroxylamine hydrochloride (136 mg, 1.67 mmol) in toluene (2 mL), diethyl aluminum chloride (1M in toluene, 1.67 mL, was introduced dropwise) 1.67 mmol). After 10 minutes, 2 - [[5- [5- (trifluoromethyl) -1,2,4-0xadiazole-3-1yl] -2-thienyl] methyl] -1,2,4-triazolo-3-carboxylate was added methyl (150 mg, 0.41 mmol) and the mixture was heated for 12 hours at
[0229] [0229] 1H NMR (400 MHz, CDCl3) 5 ppm: 7.95 (s, 1H), 7.75 (d, 1H), 7.35 (d, 1H), 6.12 (s, 2H), 3.97 (s, 3H).
[0230] [0230] Example 5: This example illustrates the preparation of 1- [[5- [5- (trifluoromethyl) -1,2,4-0xadiazol-3-yl] -2-thienyl] methyl] pyrazole-3-carboxylate methyl (Compound 1.53 from Table 71).
[0231] [0231] A mixture of 3- [5- (bromomethyl) -2-thienyl] -5- (trifluoromethyl) -1,2,4-0xadiazole (1.0 g, 3.2 mmol), 1H-pyrazole-3 -methyl carboxylate (600 mg, 4.8 mmol) and potassium carbonate (880 mg, 6.4 mmol) in acetonitrile (32 mL) was heated to 110 ° C for 2 hours. The orange suspension was filtered to remove the solids and the filtrate solution was then concentrated under reduced pressure. The resulting impure residue was purified by flash chromatography on silica gel using a cyclohexane / ethyl acetate gradient to give 610 mg of the title compound as a white solid. LC / MS (Method A) retention time = 1.00 minutes, 359 (M + H).
[0232] [0232] 1H NMR (400 MHz, CDCl3) 5 ppm: 7.78 (d, 1H), 7.51 (d, 1H), 7.12 (d, 1H), 6.89 (d, 1H), 5.61 (s, 2H), 3.98 (s, 3H).
[0233] [0233] o 2 - [[5- [5- (trifluoromethyl) -1,2,4-0xadiazol-3-yl] -2-thienyl] methyl] pyrazole-3-carboxylate (Compound 1.54 from Table T1) was isolated as a by-product as a white solid (274 mg), LC / MS (Method A) retention time = 1.10 minutes, 359 (M + H). “X F CA Ss N OBS AT
[0234] [0234] 1H NMR (400 MHz, CDCl3) 5 ppm: 7.72 (d, 1H), 7.58 (d, 1H), 7.18 (d, 1H), 6.89 (d, 1H), 6.05 (s, 2H), 3.98 (s, 3H).
[0235] [0235] Example 6: This example illustrates the preparation of 1- [[5- [5- (trifluoromethyl) -1,2,4-0xadiazol-3-yl] -2-thienyl] methyl] pyrazole-3-carboxylate ethyl (Compound 1.42 from Table T1).
[0236] [0236] In a solution of 1 - [[5- [5- (trifluoromethyl) -1,2,4-oxadiazol-3-yl] -2-thienyl] methyl] pyrazolo-3-carboxylate (100 mg, 0.27 mmol) and ethanol (0.83 mL) concentrated sulfuric acid (0.01 mL) was introduced. The white suspension was stirred for 2 hours at reflux, during which time it became a clear solution. The resulting reaction mixture was concentrated under reduced pressure and the resulting crude residue was purified by reverse phase column chromatography using a gradient of water / acetonitrile eluent to give 20 mg of the title compound as a white solid. mp: 120-124 ° C; LC / MS (Method A) retention time = 1.07 minutes, 373 (M + H).
[0237] [0237] 1H NMR (400 MHz, CDCl3) 5 ppm: 7.71 (d, 1H), 7.52 (d, 1H), 7.12 (d, 1H), 6.85 (d, 1H), 5.62 (s, 2H), 4.45 (q, 2H), 1.45 (t, 3H)
[0238] [0238] Example 7: This example illustrates the preparation of N, N-dimethyl-2 - [[5- [5- (trifluoromethyl) -1,2,4-0xadiazol-3-yl] -2-thienyl] methyl] pyrazole-3-carboxamide (Compound 1.58 from Table 71). To H.07 o F No
[0239] [0239] In a clear solution of N-methylmethanamine hydrochloride (136 mg, 1.67 mmol) in toluene (2 mL), diethyl aluminum chloride (1M in toluene, 1.67 mL, 1, was introduced dropwise) 67 mmol). After 10 minutes, 2 - [[5- [5- (trifluoromethyl) -1,2,4-0xadiazole-3-1l] -2-thienyl] methyl] -pyrazolo-3-carboxylate (150 mg, 0.41 mmol) and the mixture was heated for 12 hours at 70 ° C. The reaction was inactivated with water (ca. 0.030 ml) and the suspension was concentrated under reduced pressure. The resulting residue was purified by flash chromatography on silica gel using a cyclohexane / ethyl acetate gradient to give the title compound (105 mg, 67% yield) as a yellow gum. LC / MS (Method A) retention time = 0.96 minutes, 372 (M + H).
[0240] [0240] 1H NMR (400 MHz, CDCl3) 5 ppm: 7.71 (d, 1H), 7.55 (d, 1H), 7.12 (d, 1H), 6.42 (d, 1H), 5.78 (s, 2H), 3.05 (s, 3H), 3.15 (s, 3H)
[0241] [0241] The following general procedure was performed in a combinatorial manner using appropriate building blocks (compounds of Formula (II) and (III)) to provide the compounds of Formula (1). The compounds prepared using the following combinatorial protocol were analyzed using LC / MS Method B. Rº N Rº No
[0242] [0242] By way of example, derivatives of [[5- (trifluoromethyl) -1,2,4-0xadiazol-3-yl] heteroaryl] methyl of formula (II) (0.03 mmol) in acetonitrile (1 , 0 mL) were transferred to microwave flasks containing an amine derivative of Formula (III) (0.03 mmol), potassium carbonate (0.06 mmol), and were stirred under microwave irradiation at 120 ºC for 20 minutes in the parallel microwave device. The solvent was removed under a stream of nitrogen. The resulting impure residues were solubilized in a mixture of MeOH (250 µl) and DMA (500 µl) and directly subjected to purification by preparative LC / MS which provided the compounds of Formula (1). The structures of the isomers were assigned by NMR techniques.
[0243] [0243] When necessary, enantiomerically pure final compounds can be obtained from racemic materials as appropriate by standard physical separation techniques, such as reverse phase chiral chromatography, or by stereoselective synthetic techniques (eg using chiral starting materials). Table T1: Melting point data (m.p.) and / or retention times (Tr) for compounds according to Formula (1): m o B m> Z ST 3 o = + A = = o Ss D. 3 3 Ss 2 “Ss 2 o E Er 2 1 Z o = 2 So. o o MV - 1 - [[5- [5- (romethyl trifluent) -1,2,4- oxadiaz o 115,7 1-3-1i1] - X / Wo 1,1 CLICA; 1.08 373.2 B = - 2- NO S ANA and 116.5 thienyl] 1m ethyl] pyrazole-4-carboxyl ethyl actuate TRE à ê ê E ES is o = o = 3- [5- (1,2,4-triazol-1-ylmethyl) 1.2 thienyl] l- / “W DS 0.89 302.3. A 5- (romethyl trifluid) -1,2,4- oxadiazide 5,5-dimethyl-2 - [[5- [5- (o trifluid; and 1.3 romethyl) ODAS F 1.04 348.2 A -1,2,4- A, lys oxadiazis 1-3-yl] - 2- thienyl] mm "om - ST - o = + 4 = vs>. = Sc - aeso 4 = q = - so 5 2 Peg jo Ss ethyl] iso xazolidi n-3-one N, N-dimethyl-1 - [[5- [5- (romethyl trifluent) 1,2,4- S ne 3 7 = e 113 - 1,4 oxadiazon CDA 116 L-3- ON 2- thienyl] lm ethyl] - 1,2,4-triazole-3-amine 3- [5- t. [(4- ur
[0244] [0244] Leaf discs or leaf segments of various plant species are cut from plants grown in a greenhouse. The disks or cut leaf segments are placed in multi-well plates (24-well format) on agar water. The leaf discs are sprayed with a test solution before (preventive) or after (curative) inoculation. The compounds to be tested are prepared as solutions in DMSO (max. 10 mg / ml) which are diluted to the appropriate concentration with 0.025% Tween20 just before spraying. The inoculated leaf discs or segments are incubated under defined conditions (temperature, relative humidity, light, etc.), according to the respective test system. A single assessment of the disease level is performed 3 to 14 days after inoculation, depending on the pathosystem. The percentage of disease control in relation to untreated check leaf discs or segments is then calculated. General examples of liquid culture tests on well plates:
[0245] [0245] Fragments of mycelia or conidium suspensions of a fungus freshly prepared from liquid cultures of the fungus or from cryogenic storage are directly mixed in nutrient broth. The DMSO solutions of the test compound (max. 10 mg / mL) are diluted with 0.025% Tween20 of a factor of 50, and 10 µl of this solution is pipetted into a microtiter plate (96-well format). The nutrient broth containing the fungal spores / mycelium fragments is then added to generate a final concentration of the tested compound. The test plates are incubated in the dark at 24 ºC and 96% relative humidity. The inhibition of fungal growth is determined photometrically after 2 to 7 days, depending on the pathosystem, and the percentage of antifungal activity is calculated in relation to the untreated control. Example 1: Fungicidal activity against Puccinia recondita f. sp. tritici / wheat / preventive on leaf discs (brown rust)
[0246] [0246] Leaf segments of wheat cv. Kanzler was placed on agar in multi-well plates (24-well format) and sprayed with the formulated test compound, diluted in water. The leaf discs were inoculated with a spore suspension of the fungus 1 days after application. The inoculated leaf segments were incubated at 19% and relative humidity (ur) of 75% under a light regime of 12 hours of light / 12 hours of darkness in an air-conditioned chamber, and the activity of a compound was evaluated as a percentage of control of the disease compared to the absence of treatment when an appropriate level of damage caused by the disease appears in untreated check leaf segments (7 to 9 days after application).
[0247] [0247] The following compounds at 200 ppm in the applied formulation provide disease control of at least 80% in this test compared to untreated control leaf discs under the same conditions, which show extensive disease development.
[0248] [0248] Compounds (from Table T1) 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.10, 1 , 11, 1.12, 1.13, 1.14, 1.16, 1.17, 1.18, 1.19, 1.21, 1.22, 1.23, 1.24, 1.25 , 1.26, 1.30, 1.32, 1.33, 1.34, 1.35, 1.36, 1.37, 1.38, 1.39, 1.40, 1.41, 1 , 42,
[0249] [0249] Leaf segments of wheat cv. Kanzler is placed on agar in multi-well plates (24-well format). The leaf segments are then inoculated with a spore suspension of the fungus. The plates were stored in the dark at 19 ºC and 75% relative humidity. The formulated test compound diluted in water was applied 1 day after inoculation. The leaf segments were incubated at 19 ºC and 75% relative humidity under a 12-hour light / 12-hour dark regime in an air-conditioned chamber, and the activity of a compound was evaluated as a percentage of disease control in comparison with the absence of treatment when an appropriate level of damage caused by the disease appears in untreated leaf control segments (6 to 8 days after application).
[0250] [0250] The compounds that follow 200 ppm in the applied formulation provide at least 80% disease control in this test compared to untreated leaf control discs under the same conditions, which show extensive disease development.
[0251] [0251] Compounds (from Table T1) 1.1, 1.2, 1.4, 1.6, 1.8, 1.9, 1.11, 1.13, 1.14, 1.16, 1 , 17, 1.19, 1.21, 1.22, 1.23, 1.24, 1.25, 1.30, 1.32, 1.33, 1.34, 1.35, 1.36 , 1.37, 1.38, 1.39, 1.40, 1.41, 1.42, 1.43, 1.44, 1.45, 1.46, 1.47, 1.48, 1 , 49, 1.50, 1.51, 1.52, 1.53, 1.54, 1.55, 1.56, 1.57, 1.58, 1.59, 1.60, 1.61 , 1.63, 1.64, 1.66, 1.68, 1.70, 1.73, 1.79, 1.82, 1.83, 1.84, 1.85, 1.88, 1 , 91, 1.94, 1.95, 1.96, 1.98, 1,100, 1,101, 1,102, 1,103, 1,105, 1,106, 1,109, 1,113, 1,120, 1,122, 1,126, 1,128, 1,129, 1,130, 1,137, 1,140 , 1,144, 1,145, 1,151, 1,153, 1,158, 1,160, 1,161, 1,164, 1,166, 1,168, 1,169, 1,176 and 1,177. Example 3: Fungicidal activity against Phakopsora pachyrhizi / soy / preventive on leaf discs (Asian soybean rust)
[0252] [0252] Soy leaf disks are placed on water agar in multi-well plates (24-well format) and sprayed with the formulated test compound diluted in water. One day after application, the leaf discs are inoculated by spraying with a spore suspension on the lower leaf surface. After an incubation period in an air-conditioned chamber of 24-36 hours in the dark, at 20 ºC and u.r. of 75%, the leaf discs are kept at 20 ºC with 12 h of light / day and u.r. 75%. The activity of a compound is evaluated as a percentage of disease control compared to the absence of treatment when an appropriate level of damage caused by the disease appears in untreated leaf control discs (12 to 14 days after application).
[0253] [0253] The compounds following 200 ppm in the applied formulation provide disease control of at least 80% in this test compared to untreated leaf control discs under the same conditions, which show extensive disease development.
[0254] [0254] Compounds (from Table T1) 1.1, 1.4, 1.6, 1.13, 1.14, 1.17, 1.19, 1.21, 1.23, 1.24, 1 , 25, 1.30, 1.32, 1.33, 1.34, 1.35, 1.38, 1.39, 1.40, 1.41, 1.42, 1.43, 1.44 , 1.45, 1.46, 1.47, 1.48, 1.49, 1.50, 1.51, 1.52, 1.53, 1.54, 1.55, 1.56, 1 , 57, 1.58, 1.59, 1.60 and 1.61. Example 4: Fungicidal activity against Glomerella lagenarium (Colletotrichum lagenarium) liquid / cucumber / preventive culture (Anthracnose)
[0255] [0255] Conidia of the cryogenic storage fungus are directly mixed in nutrient broth (PDB - potato broth and dextrose). After placing a solution (DMSO) of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 ºC and the inhibition of growth is determined photometrically 3 to 4 days after application.
[0256] [0256] The compounds that follow 20 ppm in the applied formulation provide at least 80% disease control in this test compared to the untreated control under the same conditions, which has extensive disease development.
[0257] [0257] Compounds (from Table T1) 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.10, 1 , 11, 1.12, 1.13, 1.14, 1.15, 1.16, 1.17, 1.18, 1.19, 1.20, 1.21, 1.22, 1.23 , 1.24, 1.25, 1.26, 1.27, 1.28, 1.29, 1.30, 1.31, 1.32, 1.33, 1.34, 1.35, 1 , 36,
1.37, 1.38, 1.39, 1.40, 1.41, 1.42, 1.43, 1.44, 1.45, 1.46, 1.47, 1.48, 1, 49, 1.50, 1.51, 1.52, 1.53, 1.54, 1.55, 1.56, 1.57, 1.59, 1.60, 1.61, 1.62, 1.64, 1.66, 1.68, 1.70, 1.71, 1.73, 1.79, 1.82, 1.84, 1.85, 1.88, 1.91, 1, 94, 1.95, 1.96, 1.98, 1,100, 1,101, 1,102, 1,103, 1,105, 1,106, 1,109, 1,115, 1,120, 1,122, 1,126, 1,128, 1,129, 1,130, 1,137, 1,140, 1,144, 1,145, 1,149, 1,151, 1,153, 1,155, 1,156, 1,157, 1,158, 1,159, 1,160, 1,161, 1,162, 1,163, 1,164, 1,165, 1,166, 1,167, 1,168 and 1,169.

权利要求:
Claims (15)
[1]
1. Compound of Formula (1): Rº Ed
Z AN Lt F (1) characterized by A being selected from A-1, A-2 or A-3; Ss Ss
MI A DR (A-1) (A-2) (A-3) R! and R2 independently represent hydrogen, methyl, ethyl, fluorine, cyano, difluoromethyl or trifluoromethyl; and Z is selected from Z !, 7th or Z3; where 7!) represents a 4- to 6-membered non-aromatic heterocyclic ring containing 1 nitrogen in the ring, where the heterocyclyl optionally comprises 1 or 2 additional members in the ring independently selected from N, O, S, C (0) and S (0)> provided that the heterocyclyl ring cannot contain 2 contiguous atoms selected from O and S, or the heterocyclyl optionally comprises 1 additional member in the NR3 ring, where the heterocyclyl is optionally substituted by 1 or 2 substituents, which can be the same or different, selected from Rº, and in which the heterocyclyl is additionally linked to the rest of the molecule through nitrogen in the ring; Rô represents hydrogen, hydroxy, amino, formyl, C1-3 alkyl, C1.3 alkoxy, C1.3 alkyl carbonyl, C1.3-carbonyl alkoxy, N-C1-3 alkyl-aminocarbonyl, N, N-C1-3 alkyl - aminocarbonyl, N-alkoxy C1.3-aminocarbonyl, N-alkyl C1.3-
N-C1.3-aminocarbonyl, C1.2-sulfonyl alkyl, N-C1-2-aminosulfonyl, N, N-C1-2-aminosulfonyl, C1.2-dicarbonyl alkyl, C1-2-dicarbonyl alkoxy , N-C1 alkyl. 2aminodicarbonyl or N, N-N-dialkyl C1.2-aminodicarbonyl; Rº represents cyan, halogen, hydroxy, amino, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, N-methylamino or N, N-dimethylamino; Z represents a 5- or 6-membered heteroaryl ring containing 1 nitrogen in the ring, where the heteroaryl optionally comprises 1, 2 or 3 additional ring members independently selected from O, S or N, and where the heteroaryl is optionally substituted by: 1 or 2 substituents selected from R5, 1 substituent selected from R6, or 1 substituent selected from Rº and 1 substituent selected from Rº, in which additionally the heteroaryl is linked to the rest of the molecule through nitrogen in the ring; Rh represents hydroxyl, amino, cyano, halogen, formyl, nitro, C1.4 alkyl, C1.4 alkoxy, C3.4 alkenyl, C3.4 alkynyl, C34-Oxy alkenyl, C314-Oxy alkynyl, C1.2 cyanoalkyl, haloalkyl C1.2, C1.2 hydroxyalkyl, C1.2 alkoxy-C1-2 alkyl, C1-2 alkoxy C1-2 alkyl C12, N, N-dimethylamino, C1-3 alkoxy-C1-2alkylalkylalkyl, C1-3-carbonyloxyalkyl C1.2, N-alkyl C13-aminocarbonylalkyl C1-2, N, N-dialkyl C1.3-aminocarbonylalkyl C1.2, C1.2-alkyl sulfonyl, C1.3-carbonyl alkyl, C1-3 alkyl-dicarbonyl, alkoxy Ci.3-dicarbonyl, N-C1.3-alkyl-aminodicarbonyl or N, N-N-dialkyl-C1.3-aminodicarbonyl; or R5 represents -C (O) N (Ra) (Rb), where: Rº represents hydrogen, C1-.6 alkyl, C3.4 alkenyl, C3-1 alkynyl, C1.3 haloalkyl, C3.4 haloalkenyl, alkoxy C1.4, alkoxy
C1-2-C1.3 alkyl, C2.3 haloalkoxy, C3.4-alkenyl, C3-14-alkynyl, N-C1.3-amino alkyl, or N, N-C1.2-amino dialkyl; or Ra represents C3-s5 cycloalkyl, C3.sycloalkyl-C1.2 alkyl, phenyl, phenylalkyl C1.2, heterocyclyl, where the heterocyclyl unit is a 4- to 6-membered non-aromatic ring comprising 1 or 2 independently selected heteroatoms of N, O or S, provided that the heterocyclyl cannot contain 2 contiguous atoms selected from O and S, heteroaryl or C12 heteroarylalkyl, where the heteroaryl moiety is a 5- or 6-membered aromatic ring comprising 1, 2, 3, or 4 heteroatoms individually selected from N, O and S; wherein cycloalkyl, phenyl, heterocyclyl or heteroaryl is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from hydroxyl, amino, formyl, acyl, cyano, halogen, methyl, trifluoromethyl, methoxy, or N, N - dimethylamino, and where when Rº represents cycloalkyl or heterocyclyl, these cycles optionally contain 1 group selected from C (0) or S (0); and Rº represents hydrogen, methyl, ethyl, propyl, prop-2-enyl, prop-2-inyl, cyclopropyl or cyclopropylmethyl; or Rº and Ro, together with the nitrogen atom they share, form an azetidinyl, pyrrolidinyl, isooxazolidinyl, morpholino, piperazin-4-yl or piperidinyl ring optionally substituted by 1 or 2 selected groups of halogen, methyl, ethyl or methoxy ; or R5 represents -C (0) O-Rºe, where: Re represents hydrogen, C1.6 alkyl, C3.salkenyl, C3-5 alkynyl, C1.3 haloalkyl, C3.4 haloalkenyl, N, N-dialkyl C1 .3- C1-.3 aminoalkyl, C3-6 cyclolyl, C3.14-cycloalkyl
C1-2, phenyl, heterocyclyl, where the heterocyclyl unit is a 4- to 6-membered non-aromatic ring comprising 1 or 2 heteroatoms independently selected from O, S and N, provided that the heterocyclyl cannot contain 2 contiguous atoms selected from O and S, heteroaryl, where the heteroaryl moiety is a 5- or 6-membered aromatic ring comprising 1, 2 or 3 heteroatoms individually selected from N, O and S; and wherein cycloalkyl, phenyl, heterocyclyl or heteroaryl is optionally substituted by 1 or 2 substituents, which can be the same or different, selected from hydroxyl, amino, formyl, methylcarbonyl, cyano, halogen, methyl, trifluoromethyl, methoxy, or N, N-dimethylamino, and where when Rº represents cycloalkyl or heterocyclyl, these cycles optionally contain 1 group selected from C (0) or S (0)>; or R5 represents -N (R%) (Re) or -C1.2-N (R9) alkyl (Re), where Ri represents C1.3 alkyl, C34 alkenyl, C31 alkynyl, methylcarbonyl, methoxycarbonyl, N-methylaminocarbonyl, N, N-dimethylaminocarbonyl, N-methoxyminocarbonyl, N-methyl- N-methoxy-aminocarbonyl, methylsulfonyl, N-methylaminosulfonyl, N, N-dimethylaminosulfonyl, methylldicarbonyl, N-methylaminodicarbonyl or N, N-dimethylaminodicarbonyl; and Re represents hydrogen, methyl, ethyl or propyl; or Ri and Re, together with the nitrogen atom they share, form an azetidinyl, pyrrolidinyl, iso-oxazolidinyl, morpholino, piperazin-4-yl or piperidinyl ring optionally substituted by 1 or 2 selected groups of halogen, methyl, ethyl or methoxy ; or
Rº represents -CH = N (R!), Where Rf represents C1-4 alkyl, C1.4 alkoxy, C2.4 alken or C2.4 alkoxy; R6º represents C3-6 cycloalkyl, phenyl, heteroaryl, in which the heteroaryl unit is a 5- or 6-membered aromatic ring comprising 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl, in which the unit heterocyclyl is a 4- to 6-membered non-aromatic ring comprising 1 or 2 heteroatoms individually selected from N, O eS, and in which cycloalkyl, phenyl, heteroaryl and heterocyclyl are optionally substituted by 1 or 2 substituents, which can be the same or different, selected from hydroxyl, amino, formyl, acyl, cyano, halogen, methyl, trifluoromethyl, methoxy, N, N-dimethylamino, and where when Ró represents cycloalkyl or heterocyclyl, these cycles optionally contain 1 group selected from C (0) or S (0)>; and 73 represents a heterobicyclyl which is a 7 to 9 membered saturated, partially saturated or aromatic fused ring or saturated spirocyclic ring system containing 1 nitrogen, wherein the heterobicyclyl optionally comprises 1 or 2 additional members on the ring independently selected from N, O, S , C (0) and S (0)>, provided that the heterobicyclyl cannot contain 2 contiguous atoms selected from O and S, where the heterobicyclyl is optionally substituted by 1 substituent selected from R7, and in which additionally the heterobicyclyl is linked to the rest of the molecule through nitrogen in the ring; and Rº is cyan, fluorine, chlorine, amino, hydroxy, methyl, difluoromethyl, trifluoromethyl, methoxy, N, N-dimethylamino,
formyl, methylcarbonyl, methoxycarbonyl, N-methylaminocarbonyl or N, N-dimethylaminocarbonyl; or a salt or N-oxide thereof.
[2]
Compound according to claim 1, characterized in that A is A-11.
[3]
Compound according to any one of claims 1 and 2, characterized in that R 'and R2 are hydrogen.
[4]
Compound according to any one of claims 1, 2 and 3, characterized in that Z is Z! selected from:
RO A AA OX
DO OQ O O Che e (= Cd% O. - or where Z! Is optionally substituted by 1 or 2 substituents, which can be the same or different, selected from Rº.
[5]
Compound according to claim 4, characterized in that Rº is selected from methyl or ethyl.
[6]
Compound according to any one of claims 1, 2 and 3, characterized in that Z is 7 ° selected from: A “A A A.
AND SO ED.
2 nº NNZ PN nº where 7º is optionally substituted by: 1 or 2 substituents selected from R5, 1 substituent selected from Rº or 1 substituent selected from Rº and 1 substituent selected from Rº.
[7]
Compound according to claim 6, characterized in that R ° is independently selected from hydroxy, amino, cyano, halogen, formyl, nitro, C1-4 alkyl, C1.4 alkoxy, C1.2 haloalkyl, C1.2 alkoxy alkyl C1.2, N, N-dimethylamino, -C (0) O-Rº where Re is Cia alkyl and - C (O) N (Ra) (Rº), where Rº is selected from hydrogen, C1- alkyl 14 or C1.4 alkoxy, and Rº is selected from hydrogen or methyl; and Rº is phenyl optionally substituted by 1 or 2 substituents, which can be the same or different, selected from hydroxyl, methyl, methoxy, cyano, fluorine, chlorine or bromine.
[8]
8. Compound according to claim 7, characterized in that Rº is selected from amino, cyano, chlorine, fluorine, formyl, nitro, methyl, ethyl, difluoromethyl, methoxymethyl, N, N-dimethylamino, methoxycarbonyl, ethoxycarbonyl or n-propoxycarbonyl ; and D is phenyl optionally substituted by 1 or 2 substituents, which may be the same or different, selected from fluorine, chlorine or bromine.
[9]
Compound according to any one of claims 6, 7 and 8, characterized in that 2 ° is optionally substituted by 1 or 2 substituents selected from R5.
[10]
Compound according to any one of claims 1, 2 and 3, characterized in that Z is Z3 selected from:
The CO or CD where Z3 is optionally substituted by 1 substituent selected from R '.
[11]
Compound according to claim 10, characterized in that R7 is selected from hydroxyl, methoxy, methyl, cyano, fluorine or chlorine.
[12]
Agrochemical composition characterized by comprising a fungicidal effective amount of a compound of Formula (1) according to any one of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 and 11.
[13]
Composition according to claim 12, characterized in that it further comprises at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.
[14]
14. Method for controlling or preventing infestation of useful plants by phytopathogenic microorganisms, characterized by a fungicide-effective amount of a compound of Formula (TI) according to any one of claims 1, 2, 3, 4 , 5, 6, 7, 8, 9, 10 and 11, or a composition comprising this compound as an active ingredient to be applied to plants, their parts or their location.
[15]
Use of a compound of Formula (TI) according to any one of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, and 11, characterized in that it is as a fungicide.

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同族专利:

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公开号 | 公开日

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IL269023A|2021-12-01|

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US20200277287A1|2020-09-03|

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CL2019002512A1|2019-11-29|

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CN110382492A|2019-10-25|

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CO2019009262A2|2019-08-30|

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IL269023D0|2019-10-31|

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WO2018158365A1|2018-09-07|

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法律状态:
2021-11-03| B350| Update of information on the portal [chapter 15.35 patent gazette]|

优先权:

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申请号 | 申请日 | 专利标题

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EP17159202|2017-03-03|

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EP17159202.5|2017-03-03|

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EP17160411|2017-03-10|

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EP17160411.9|2017-03-10|

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IN201711043196|2017-12-01|

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IN201711043196|2017-12-01|

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PCT/EP2018/055042|WO2018158365A1|2017-03-03|2018-03-01|Microbiocidal oxadiazole derivatives|

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