fungicidal compositions

专利摘要:
A fungicidal composition comprising a mixture of an N-phenylamidine defined by formula (I) as component (A) and another pesticide as component (B) as defined in claim 1, as well as the use of the composition in agriculture or horticulture to control or prevent plant infestation by phytopathogenic microorganisms, preferably by fungi.
公开号:BR112019026331A2
申请号:R112019026331-4
申请日:2018-06-07
公开日:2020-07-21
发明作者:Matthias Weiss；Sarah Sulzer-Mosse
申请人:Syngenta Participations Ag；
IPC主号:

专利说明:

[001] [001] The present invention relates to new fungicidal compositions, their use in agriculture or horticulture to control diseases caused by phytopathogens, especially phytopathogenic fungi, and to methods of controlling diseases in useful plants, especially fruits and vegetables.
[002] [002] Certain phenylamidine derivatives have been proposed in the literature as microbicidal active ingredients in pesticides. For example, WO 00/46184 and WO 03/093224 disclose phenylamidines which are described as being useful as fungicides. However, the biological properties of these known compounds and their compositions are not entirely satisfactory for controlling or preventing plant infestation by phytopathogenic fungi. In addition, while many fungicidal compounds and compositions, belonging to several different chemical classes, have been / are being developed for use as fungicides in useful plant cultures, crop tolerance and activity against particular pathogenic fungi does not always meet the needs of agricultural practice in many ways.
[003] [003] There is, therefore, a continuing need to find new compounds and new compositions with superior properties for use in the control or prevention of plant infestation by phytopathogenic fungi; for example, compounds having a greater biological activity, an advantageous activity spectrum, an increased safety profile, improved physico-chemical properties, increased biodegradability, or compositions having a broader activity spectrum, improved crop tolerance, synergistic interactions or properties enhancers, or compositions that exhibit a faster onset of action or that have residual activity of longer duration or that allow a reduction in the number of applications and / or a reduction in the application rate of the compounds and compositions required for the effective control of a phytopathogen, thus allowing “beneficial resistance management practices, reduced environmental impact and reduced operator exposure.
[004] [004] The use of compositions comprising mixtures of different fungicidal compounds can address some of these needs (eg combining fungicides with different activity spectra). However, it is especially advantageous if, in such mixing compositions, one or more of the fungicidal compounds themselves have favorable fungicidal properties.
[005] [005] The present invention therefore provides new fungicidal compositions comprising as active ingredients a mixture of component (A) and component (B), wherein component (A) is a compound of formula (1) CH; R Sen, 2
[006] [006] Rº is ethyl, isopropyl or cyclopropyl (preferably ethyl or isopropyl); and
[007] [007] R is —CH2C (= N-OC2Hs5) CH3, n-butoxymethyl, cyclopropyl, cyclobutylmethoxymethyl, cyclopentoxymethyl, -
[6] [6] Cc F 3 (difluoromethyl) -1-methyl-N- [(3R) -1,1,3-trimethylindan-4-yl] pyrazole-4-carboxamide FR
[6] [6] Mancozebe 5 5
[008] [008] or a salt, enantiomer, tautomer or N-oxide thereof; and wherein the weight ratio of component (A) to component (B) is 40: 1 to 1:40.
[009] [009] In general, the weight ratio of component (A) to component (B) can be from 1000: 1 to 1: 1000, especially from 50: 1 to 1:50, more especially in a ratio of 40: 1 to 1:40, even more especially at a ratio of 20: 1 to 1:20, even more especially still from 10: 1 to 1:10, and most especially from 5: 1 and 1: 5. Particular preference is given to a ratio of 2: 1 to 1: 2, and a ratio of 4: 1 to 2: 1 is also especially preferred. Specific individual ratios that are preferred include the ratios of 1: 1, 5: 1, 5: 2, 5: 3, 5: 4, 4: 1, 4: 2, 4: 3, 3: 1, 3: 2, 2: 1, 1: 5, 2: 5, 3: 5, 4: 5, 1: 4, 2:94, 3: 4, 1: 3, 2: 3, 1: 2, 1: 600, 1: 300, 1: 150, 1: 100, 1:50, 1; 40, 1:35, 1:20, 2:35, 4:35, 1:10 1:75, 2:75, 4:75, 1 : 6000, 1: 3000, 1: 1500, 1: 350, 2: 350, 4: 350, 1: 750, 2: 750 and 4: 750.
[0010] [0010] The compounds of formula (I), which are present in the compositions of the invention, have favorable fungicidal properties. Such benefits may include, inter alia, advantageous levels of biological activity to protect plants against diseases that are caused by fungi, or superior properties for use as agrochemical active ingredients (eg increased biological activity, an advantageous spectrum of activity, a profile increased safety, improved physico-chemical properties, or increased biodegradability).
[0011] [0011] The presence of one or more possible asymmetric carbon atoms in a compound of formula (1) means that the compounds can occur in optically isomeric forms, that is, enantiomeric or diastereomeric forms. The specific substitution pattern on the carbon atom to which R2 is attached means that the compounds of formula (I) occur in (at least) two enantiomeric forms. Atropisomers may also occur as a result of restricted rotation around a single bond. The present invention includes all of these possible isomeric forms (e.g., geometric isomers) and their mixtures for a compound of formula (IT). Likewise, formula (1) is intended to include all possible tautomers. The present invention includes all possible tautomeric forms for a compound of formula (1), and also a racemic compound, that is, a mixture of at least two enantiomers in a substantially 50:50 ratio.
[0012] [0012] In each case, the compounds of formula (1) according to the invention are in free form, in oxidized form as an N-oxide or in salt form, e.g. , an agronomically usable form of salt.
[0013] [0013] 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.
[0014] [0014] Preferably, component (A) is a compound selected from compounds Q.001, Q.002, Q.003, Q.004, Q.005, Q.006, 90.007, Q.008, 9.009 and 9.010, as defined in Table Q below: Table Q
[0015] [0015] Preferably, component (B) is a compound selected from the group consisting of (B12) a compound selected from the group consisting of: Azoxystrobin (CAS No.: 131860-33-8), Trifloxystrobin (CAS No.: 141517- 21-7), Picoxystrobin (CAS No: 117428-22-5), 1- [2 - [[1- (4-chlorophenyl) pyrazol-3-yl] oxymethyl] -3-methyl-phenyl] - 4- methyl-tetrazol-5-one (from WO 2013/162072), Coumoxystrobin (CAS No.: 850881-70-8), Ciproconazole (CAS No.: 94361-06-5), Difenoconazole (CAS No.: 119446-68 -3), Tebuconazole (CAS No.: 107534-96-3), Protioconazole (CAS No.: 178928-70-6) Hexaconazole (CAS No.: 79983-71-4), Mefentrifluconazole (CAS No.: 1417782-03 -6; (2RS) -2- [4- (4-chlorophenoxy) -a, a, a-trifluoro-o-tolyl] -1- (1H-1,2,4-triazol-1-yl) propan- 2-01l; de WO 2013/007767), Fenpropidina (CAS No.: 67306-00-7), Fenpropimorph (CAS No.: 67564-91-4), Bixafen (CAS No.: 581809-46-3), Fluxapyroxade (CAS No.: 907204-31-3), Isopyrazam (CAS No.: 881685-58-1), Sedaxane (CAS No.: 874967-67-6), Benzovindiflupir (CAS No.: 1072957 -71-1), Pidiflumetofeno (Nº. CAS: 1228284-64-7), 3- (difluoromethyl) - 1-methyl-N - [(3R) -1,1,3-trimethylindan-4-yl] pyrazole-4-
[0016] [0016] Most compounds of component (B) are referred to above by the so-called "common ISO name" or another "common name" is used in individual cases or a brand name. The compounds of component (B) are known and are commercially available and / or can be prepared using procedures known in the art and / or procedures reported in the literature.
[0017] [0017] For example:
[0018] [0018] "Isabion" TM (CAS number 9015-54-7) is commercially available as a biostimulating protein hydrolyzate.
[0019] [0019] Taegro is a biofungicide comprising the FZB24 strain of Bacillus subtilis var. amyloliquefaciens).
[0020] [0020] Serenadeo is a biofungicide from Bacillus subtilis based on the QOST713 strain.
[0021] [0021] Subtilexo is a biofungicide from Bacillus subtilis based on the MBI600 strain.
[0022] [0022] Methods for producing lolino alkaloids are known in the art. WO2008 / 111861 describes methods for extracting alkaloids from lolins from plant material infected with endophytes. Blankenship et al. ((2001) Phytochemistry 58, 395-401) describe the production of lolino alkaloids by fermentation of fungal endophytes in chemically defined growth media. Preferred alkali compositions of lolins are obtained by the processes described in WO2016091987.
[0023] [0023] The compounds X.01, X.02, X.03, X.04, X.05, X.06 X.07, X.08, X.09, X.10, X.11, X. 12, X.13, X.14, X.15, X.16, X.17, X.18, X.19, X.20, X.21, X.22 and X.23 in Table X above can be prepared according to the procedures described in WO 2017/055473.
[0024] [0024] Compounds Y.01, Y.02, Y.03, Y.04, Y.05, Y.06, Y.07, Y.08, Y.09, Y.10, Y.11, Y .12, Y.13, Y.14, Y.15, Y.l16, Y.17, Y.18 and Y.19 in Table Y above can be prepared according to the procedures described in WO 2017/093348.
[0025] [0025] 1- [2 - [[1- (4-chlorophenyl) pyrazol-3-yl] oxymethyl] -3-methyl-phenyl] -4-methyl-tetrazol-5-one can be prepared according to procedures described in WO 2013/162072.
[0026] [0026] Mefentrifluconazole (CAS #: 1417782-03-6; (2RS) -2- [4- (4-chlorophenoxy) -a, a, a-trifluoro-o-tolyl] -1- (1H- 1, 2,4-triazol-1-yl) propan-2-ol) can be prepared according to the procedures described in WO 2013/007767.
[0027] [0027] 3- (difluoromethyl) -l-methyl-N - [(3R) -1,1,3-trimethylindan-4-yl] pyrazolo-4-carboxamide can be prepared according to the procedures described in WO 2011 / 162397.
[0028] [0028] Isofluciprame (CAS No.: 1255734-28-1; N - [(5-chloro-2-isopropyl-phenyl) methyl] -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-l-methyl -pyrazolo-4-carboxamide) can be prepared according to the procedures described in WO 2010/130767.
[0029] [0029] The structure compound can be prepared according to the procedures described in WO 2014/095675),
[0030] [0030] The structure compound can be prepared according to the procedures described in WO 2014/095675.
[0031] [0031] The structure compound: F o NO (o) | F O. (Y13149; N- [2- [2-chloro-4- (tri fluoromethyl) phenoxy] phenyl] -3- (difluoromethyl) -1-methyl-pyrazolo-4-carboxamide) can be prepared according to procedures described in WO 2015/058444.
[0032] [0032] Fluindapir (No. Cas: 1383809-87-7; a 3- (di fluoromethyl) -N- (7-fluoro-1, 1,3-trimethyl-indan-4-11) -1- methyl- pyrazolo-4-carboxamide) can be prepared according to the procedures described in WO 2012/084812.
[0033] [0033] [2- [3- [2- [1- [2- [3,5-bis (difluoromethyl) pyrazol-11-yl] acetyl] -4-piperidyl] thiazol-4-yl 1 - methanesulfonate - 4,5-dihydroisoxazol-5-yl] -3-chloro-phenyl] can be prepared according to the procedures described in WO 2012/025557.
[0034] [0034] But- 3-inyl N- [6 - [[(Z2) - [(l1-methylthetrazol-5-yl) -phenylmethyl]]] oxymethyl] -2-pyridyl] carbamate can be prepared from according to the procedures described in WO 2010/000841.
[0035] [0035] N- [(5-chloro-2-isopropyl-phenyl) methyl] -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-pyrazolo-4-carboxamide can be prepared according to the procedures described in WO 2010/130767.
[0036] [0036] N '- [4- (4,5-dichlorothiazol-2-yl) oxy-2,5-dimethyl-phenyl] -N-ethyl-N-methyl-formamidine can be prepared according to the procedures described in WO 2007/031513.
[0037] [0037] A 2 - [[3- (2-chloropheni] l) -2- (2,4-difluorophenyl) oxiran-2-yl] methyl] -4H-1,2,4-triazolo-3-thione can be prepared according to the procedures described in WO 2010/146031.
[0038] [0038] 2- [2-chloro-4- (4-chlorophenoxy) phenyl] -1- (1,2,4-triazol-11-yl) propan-2-o1 can be prepared according to the procedures described in WO 2013/024082.
[0039] [0039] 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.
[0040] [0040] 2- [2-fluoro-6 - [(8-fluoro-2-methyl-3-quinolyl) oxy] phenyl] propan-2-o0l can be prepared according to the procedures described in WO 2011/081174 .
[0041] [0041] The 4,4,5-trifluoro-3,3-dimethyl-1- (3-quinolyl) isoquinoline can be prepared according to the procedures described in WO 2005/070917.
[0042] [0042] 3- (difluoromethyl) -N- (7-fluoro-1,3,3-trimethyl-indan-4-11) -1-methyl-pyrazolo-4-carboxamide can be prepared according to the procedures described in WO 2012/084812.
[0043] [0043] 3- (di-fluoromethyl) -1-methyl-N- (1,1,3-trimethylindan-4-yl) pyrazolo-4-carboxamide can be prepared according to the procedures described in WO 2014/013842.
[0044] [0044] 3-chloro-6-methyl-5-phenyl-4- (2,4,6-trifluorophenyl) pyridazine can be prepared according to the procedures described in WO 2005/121104.
[0045] [0045] 3-chloro-4- (2,6-difluorophenyl) -6-methyl-5-phenyl-pyridazine can be prepared according to the procedures described in WO 2012/020774.
[0046] [0046] A 2- (difluoromethyl) -N- (1,1,3-trimethylindan-4-yl) pyridine-3-carboxamide, 2- (difluoromethyl) -N- (3-ethyl-11,1-dimethyl- indan-4-yl) pyridine-3-carboxamide, 2-7 (difluoromethyl) -N- (1,1-dimethyl-3-propyl-indan-4-yl) pyridine-3-carboxamide, 2- (difluoromethyl) - N- (3-isobutyl-1,1-dimethyl-indan-4-yl) pyridine-3-carboxamide, 2-7 (difluoromethyl) -N - [(3R) -1,1,3-trimethylindan-4-yl ] pyridine-3-carboxamide, 2- (difluoromethyl) -N - [(3R) -3-ethyl-1,1-dimethyl-indan-4-yl] pyridine-3-carboxamide and 27 (di-fluoromethyl) -N- [(3R) -1,1-dimethyl-3-propyl-indan-4-yl] pyridine-3-carboxamide can be prepared according to the procedures described in WO 2014/095675 and / or WO 2016/139189.
[0047] [0047] The o can be prepared according to the procedures described in WO 2003/035617.
[0048] [0048] In a preferred embodiment, composition IA comprises “as active ingredients a mixture of component (A) and component (B), wherein component (A) is a compound of formula (1) CH; R Rê
[0049] [0049] Rº is ethyl, isopropyl or cyclopropyl (preferably ethyl or isopropyl); and R2 is —-CH2C (= N-OC2Hs) CH3, n-butoxymethyl, cyclopropyl, cyclobutylmethoxymethyl, cyclopentoxymethyl, -CH2C (= CH:) CH3, n-butyl, phenyl, 2-methyl-phenyl or 3,5-difluorophenyl; or a salt, enantiomer, tautomer or N-oxide thereof; and component (B) is a compound selected from the group consisting of (Bl2) a compound selected from the group consisting of: Azoxystrobin (CAS No.: 131860-33-8), Trifloxystrobin (CAS No.: 141517-21-7) , Picoxystrobin (CAS No: 117428-22-5), 1- [2 - [[1- (4-chlorophenyl) pyrazol-3-yl] oxymethyl] -3-methyl-phenyl] -4-methyl-tetrazole- 5-one (from WO
[0050] [0050] In composition IA it is preferred that component (A) is a compound, or a salt, enantiomer, tautomer or N-oxide thereof, selected from N '- [4 - [(3E) -3-ethoxy-imino- 1-hydroxy-1- (tri-fluoromethyl) butyl] -5-methoxy-2-methyl-phenyl] -N-ethyl-N-methyl-formamidine (compound Q.001); N '- [4- [1- (butoxymethyl) -2,2,2-trifluoro-1-hydroxy-ethyl] - 5-methoxy-2-methyl-phenyl] -N-ethyl-N-methyl-formamidine (compound 0.002); N '- [4- (1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl) -5-methoxy-2-methyl-phenyl] -N-isopropyl-N-methyl-formamidine (compound 0.003) ; N '- [4- [1- (cyclobutylmethoxymethyl) -2,2,2-trifluoro-1-hydroxy-ethyl] -5-methoxy-2-methyl-phenyl] -N-ethyl-N-methyl-formamidine (compound 0.004); N '- [4- [1- (cyclopentoxymethyl) -2,2,2-trifluoro-1-hydroxy-ethyl] -5-methoxy-2-methyl-phenyl] -N-ethyl-N-methyl-formamidine (compound Q0.005); N '- [4- [1-hydroxy-3-methyl-11- (trifluoromethyl) but-3-enyl] - S5-methoxy-2-methyl-phenyl] -N-isopropyl-N-methyl-formamidine (compound 0.006 ); N '- [4- [1-hydroxy-1- (trifluoromethyl) pentyl] -5-methoxy-2-methyl-phenyl] -N-isopropyl-N-methyl-formamidine (compound
[0051] [0051] In a preferred composition of composition IA, component (A) is N '- [4 - [(3E) -3-ethoxy-imino-1-hydroxy-1- (trifluoromethyl) butyl] -5- methoxy-2-methyl-phenyl] - N-ethyl-N-methyl-formamidine (compound 9,001); or a salt, enantiomer, tautomer or N-oxide thereof.
[0052] [0052] In another preferred composition of the composition composition IA, component (A) is N '- [4- [1- (butoxymethyl) - 2,2,2-trifluoro-1-hydroxy-ethyl] -5- methoxy-2-methyl-phenyl] -N-ethyl-N-methyl-formamidine (compound Q.002); or a salt, enantiomer, tautomer or N-oxide thereof.
[0053] [0053] In another preferred composition of the composition composition IA, component (A) is N '- [4- (l-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl) -5-methoxy- 2-methyl-phenyl] -N-isopropyl-N-methyl-formamidine (compound Q.003); or a salt, enantiomer, tautomer or N-oxide thereof.
[0054] [0054] In another preferred composition of the composition composition IA, component (A) is N '- [4- [1- (cyclobutylmethoxymethyl) -2,2,2-trifluoro-1-hydroxy-ethyl] -5- methoxy-2-methyl-phenyl] -N-ethyl-N-methyl-formamidine (compound
[0055] [0055] In another preferred composition of the composition composition IA, component (A) is N '- [4- [1- (cyclopentoxymethyl) -2,2,2-trifluoro-1-hydroxy-ethyl] -5- methoxy-2-methyl-phenyl] -N-ethyl-N-methyl-formamidine (compound
[0056] [0056] In another preferred composition of the composition composition IA, component (A) is N '- [4- [11-hydroxy-3-
[0057] [0057] In another preferred composition of the composition IA modality, component (A) is N '- [4- [l-hydroxy-1- (trifluoromethyl) pentyl] -5-methoxy-2-methyl-phenyl] - N-isopropyl-N-methyl-formamidine (compound Q.007); or a salt, enantiomer, tautomer or N-oxide thereof.
[0058] [0058] In another preferred composition of composition IA, component (A) is N-isopropyl-N '- [5-methoxy-2-methyl-4- (2,2,2-trifluoro-1-hydroxy -l-phenyl-ethyl) phenyl] -N-methyl-formamidine (compound 0.008); or a salt, enantiomer, tautomer or N-oxide thereof.
[0059] [0059] In another preferred composition of the composition composition IA, component (A) is N-ethyl-N '- [5-methoxy-2-methyl-4- [2,2,2-trifluoro-1-hydroxy -1- (o-tolyl) ethyl] phenyl] - N-methyl-formamidine (compound Q0.009); or a salt, enantiomer, tautomer or N-oxide thereof.
[0060] [0060] In another preferred composition of the composition modality (TIA, component (A) is N '- [4- [1- (3,5-difluorophenyl) -2,2,2-trifluoro-1-hydroxy- ethyl] -5-methoxy-2-methyl-phenyl] -N-ethyl-N-methyl-formamidine (compound Q.010), or a salt, enantiomer, tautomer or N-oxide thereof.
[0061] [0061] The compounds of formula (1) can be prepared as shown in the following schemes, in which, unless otherwise specified, the definition of each variable is as defined above for a compound of formula (1).
[0062] [0062] The compounds of formula (I), in which R1 and R2 are as defined for formula (LI), can be obtained by treating compounds of formula (II), in which R1 is as defined for formula (1) and Hal is halogen, preferably bromine or iodine, with a metallizing agent such as n-butyl lithium, magnesium, zinc or i-propyl magnesium chloride-LiCl to generate an organometallic intermediate (II-a) which is then reacted with a carbonyl compound of formula (III), wherein R2 is as defined for formula (1). This is shown in Scheme 1 below, examples and representative conditions are described in Chem. Commun.
[0063] [0063] The compounds of formula (II), in which R! is as defined for formula (1) and Hal is halogen, preferably bromine or iodine, can be obtained by transforming a compound of formula (IV), in which Hal is halogen, preferably bromine or iodine, by various methods known among the most widely used are the following:
[0064] [0064] a) Treatment with a compound of formula (Va), where R1 is as defined for formula (1) and R11 is C1-C4 alkyl, in an inert solvent such as toluene at temperatures between 0 ºC and 100 “ºC.
[0065] [0065] b) Treatment with an orthoester of formula (V-b), where R11 is C1-C4 alkyl, followed by treatment with an amine of formula (Vc) in an organic solvent such as methanol at temperatures between 20 ºC and 100 “ºC.
[0066] [0066] c) Treatment with a formamide of formula (V-d), where R1 is as defined for formula (1) and an activating agent such as POCl3 in an inert solvent such as dichloromethane at temperatures between -20 " ºC and 40 “ºC. This is shown in Scheme 2 below.
[0067] [0067] The compounds of formula (IV), in which Hal is halogen, preferably bromine or iodine, can be obtained by halogenating a compound of formula (VI) with a reactive agent such as bromine, N-bromosuccinimide or N-iodosuccinimide in an inert solvent such as dichloromethane at temperatures between -40 ºC and 40 ºC. This is shown in Scheme 3 below.
[0068] [0068] The synthesis of anilines of formula (VI), by reducing the corresponding nitro compounds, is trivial for one skilled in the art.
[0069] [0069] Alternatively, compounds of formula (1) in which R11 and R2 are as defined for formula (1), can be obtained by transforming compounds of formula (VII), in which Rº is as defined for formula (I), by several known methods, the most widely used of which are:
[0070] [0070] a) Treatment with a compound of formula (Va), where R1 is as defined for formula (II) and R11 is C1-C4 alkyl, in an inert solvent such as toluene at temperatures between 0 ºC and 100 “ºC.
[0071] [0071] Db) Treatment with an orthoester of formula (V-b), where R11 is C1-C4 alkyl, followed by treatment with an amine of formula (Vc) in an organic solvent such as methanol at temperatures between 20 ºC and 100 ºC.
[0072] [0072] This is shown in Scheme 4 below.
[0073] [0073] The compounds of formula (VII), where Rº is as defined for formula (1), can be obtained by treating a compound of formula (VI) with a compound of formula (III) in which Rº is as defined for formula (1), under acidic conditions in an inert solvent at temperatures between 40 ºC and 200 "ºC. This is shown in the Scheme below.
[0074] [0074] Alternatively, the compounds of formula (1), in which R 'and R are as defined for formula (1), can be obtained by treating compounds of formula (VIII-a) or compounds of formula (VIII-b), with an organometallic reagent of formula (IX-a), where [ M] can be a magnesium, zinc or lithium salt among other metal salts suitable for addition to carbonyl compounds, or (IX-b), where R! º is C1i-C4a alkyl, respectively. Certain species such as zinc-based organometallic reagents of formula (IX-a) may require the addition of a Lewis acid such as Ti (OiPr) s: to add effectively to the carbonyl species. The reagents of formula (IX-b) may require the addition of a nucleophilic catalyst such as cesium fluoride to add effectively to the carbonyl species. This is shown in scheme 6.
[0075] [0075] Methods for generating organometallic reagents of formulas (IX-a) and (IX-b) are known to one skilled in the art, protocols and general references can be found in March's Advanced Organic Chemistry, Smith, 7th edition, Wiley , 2013.
[0076] [0076] The compounds of formulas (VIII-a) and (VIII-b), in which R1 and R2 are as defined for formula (1), can be obtained by treating compounds of formula (II), in which R1 is as defined for formula (1) and Hal is halogen, preferably bromine or iodine, with a metallizing agent such as n-butyl lithium, magnesium, zinc or i-propyl magnesium chloride-LiCl to generate an organometallic intermediate (II-a) which is then reacted with a carbonyl compound of formula (Xa) or (Xb), respectively, where Rº is as defined for formula (I) and X is a suitable leaving group such as fluorine, chlorine, bromine, C1- Ca alkoxy, C1-Ca alkoxycarbonyloxy, C1i-Ce alkylcarbonyloxy, phenoxy or Ní (Me) OMe, as shown in scheme 7.
[0077] [0077] Certain combinations of organometallic intermediates (II-a) and reagents (Xb) or (Xa) may require the presence of a transition metal catalyst such as CuCl or Ni (acetylacetonate) 2,; - 2,2-bipyridine as described in Angew. Chem. Int. Ed. 2006, 45, 6040 or JU. Am. Chem. Soc. 2004, 126, 15964 and references contained therein to proceed effectively.
[0078] [0078] Alternatively, certain compounds of formula (I-a), where R! ' and R2 are as defined for formula (1), X is oxygen or sulfur and Rº is C1-Cçyl alkyl, C3-C6 cycloalkyl, C3-Ce6 alkenyl, C3-Ce alkynyl, aryl (where aryl is optionally substituted with one to three groups Rº), heteroaryl (where heteroaryl is optionally substituted with one to three groups R $), arylalkyl (C1-C1) (where aryl is optionally substituted with one to three groups Rº) or heteroarylalkyl (C1-Cs «) (where the heteroaryl is optionally substituted with one to three groups Rº), can be obtained by treating compounds of formula (XI), where R 'is as defined for formula (TI), with compounds of formula (XI), where X and R ! are as defined above, in an inert solvent such as DMF in the presence of a base such as sodium hydride at temperatures between O “* C and 80“ C. This is shown in Scheme 8. Scheme 8 | | OS Ng! nn XI) LE R —— R Ad A a o (Fa) R
[0079] [0079] The compounds of formula (XI), in which R! is as defined for formula (LI), can be obtained by treating compounds of formula (VIII-a), where R! ' and Rº are as defined for formula (I), with a sulfur-ylide reagent such as trimethylsulfoxonium iodide in the presence of a base such as potassium tert-butoxide, in an inert solvent such as DSMO at a temperature between O ºC and 80 ºC. This is shown in Scheme 9. Scheme 9
[0080] [0080] The compounds of formula (1), where R 'is as defined for formula (1), can be obtained by treating compounds of formula (XXI), where X is halogen, preferably bromine or iodine, with a base such as sodium hydroxide to generate the compound (XXII), which is then reacted with a carbonyl compound of formula (VIII-a) (the preparation of which is described above), wherein R! it is as defined for formula (I), and a base such as lithium diisopropylamide. This is shown in Scheme 10 below.
[0081] [0081] Alternatively, the compounds of formula (1), where Ri and R7 are as defined for formula (1), can be obtained by transforming another closely related compound of formula (Ib) using techniques of standard synthesis known to the person skilled in the art. Non-exhaustive examples include oxidation reactions, reduction reactions, hydrolysis reactions, coupling reactions, aromatic nucleophilic or electrophilic substitution reactions, nucleophilic substitution reactions, nucleophilic addition reactions and halogenation reactions.
[0082] [0082] The term "fungicide", as used herein, designates a compound that controls, modifies or prevents the growth of fungi. The term "fungicidal effective amount" 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.
[0083] [0083] The term "plants" refers to all the physical parts of a plant, including seeds, seedlings, young plants, roots, tubers, stems, stems, foliage and fruits.
[0084] [0084] The term "plant propagating material" denotes all generative parts of a plant, for example seeds or vegetative parts of plants such as cuttings and tubers. It includes seeds in the strict sense, as well as roots, fruits, tubers, bulbs, rhizomes and plant parts.
[0085] [0085] The term "local" as used herein means fields in which, or on which, plants are grown or where 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.
[0086] [0086] Throughout this document, the term “composition” represents the various mixtures or combinations of components (A) and (B) (including the modalities defined above), for example in a simple form of “ready mix”, in a combined spray mixture made up of separate formulations of the individual active ingredient components, such as a “tank mix”, and in a combined use of the simple active ingredients when applied in a sequential manner, that is, one after the other with a relatively short period, such as a few hours or days. The order of application of the components (A) and (B) is not essential for the operation of the present invention.
[0087] [0087] The composition according to the invention is effective against harmful microorganisms, such as microorganisms that cause phytopathogenic diseases, in particular against phytopathogenic bacteria and fungi.
[0088] [0088] The composition of the invention can be used to control plant diseases caused by a broad spectrum of fungal plant pathogens in the classes of Basidiomycetes, Ascomycetes, Oomycetes and / or Deuteromycetes, Blasocladiomycetes, Critidiomycetes, Glomeromycetes and / or Mucoromycetes.
[0089] [0089] The composition is effective in controlling a wide range of plant diseases, such as leaf pathogens from ornamental crops, grasses, vegetables, fields, cereals and fruits.
[0090] [0090] These pathogens can include:
[0091] [0091] Oomycetes, including Phytophthora diseases such as those caused by Phytophthora capsici, Phytophthora infestans, Phytophthoraoyae, Phytophthora frágariae, Phytophthora nicotianae, Phytophthora nicnamiana, Phytophthora cinnamomi, Phytophthora citricola, Phytophthoray citricola; Pythium diseases such as those caused by Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare and Pythium ultimum;
[0092] [0092] Ascomycetes, including diseases of blemishes, spots, blast or rust and / or rot, for example those caused by Pleosporales such as Stemphylium solani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleosporaha herbarum, Phoospora herbarum herpotrichoides, Phaeocryptocus gaeumannii, Ophiosphaerella graminicola, Ophiobolus graminis, Leptosphaeria maculans, creberrima Hendersonia, Helminthosporium triticirepentis, Setosphaeria turcica, Drechslera glycines, Didymella bryoniae, Cycloconium oleagineum, Corynespora cassiicola, Cochliobolus sativus, Bipolaris cactivora, Venturia inaequalis, Pyrenophora teres, Pyrenophora tritici- repentis, Alternaria alternata, Alternaria brassicicola, Alternaria solani and Alternaria tomatophila, Capnodiales such as Septoria tritici, Septoria nodorum, Septoria glycines, Cercospora arachidicola, Cercospora sojina, Cercospora zeae-maydis, Cercosporella capsellae and Cercosporella capsellae and Cercosporella capsellae oides, Cladosporium carpophilum, Cladosporium effusum, Passalora fulva, Cladosporium oxysporum, Dothistroma septosporum, Isariopsis clavispora, Mycosphaerella fijiensis, Mycosphaerella graminicola, Mycovellosiella koepkeis, Phaeoispor
[0093] [0093] Basidiomycetes, including saddle bags, for example those caused by Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, ferrugens, for example those caused by Puciniales such as Cerotelium fici, Chrysomyxa arctostaiae, chrysomyxa arctostaphyleae; Puccinia arachidis, Puccinia cacabata, Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp. Hordei, Puccinia striiformis f. sp. Secalis, Pucciniastrum coryli, or Uredinales such as Cronartium ribicola, Gymnosporangium juniperi-viginianae, Melampsora medusae, Phakopsora pachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzschelia discolor and Uromyces viciae-fabae; and other rotting and diseases such as those caused by Cryptococcus spp., Exobasidium vexans, Marasmiellus inoderma, Mycena sSPpP., Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisum, Circumisisiforum, Rhinisisisisisifisis, Rhea , Entyloma dahliae, Entylomella microspora, Neovossia moliniae and Tilletia caries;
[0094] [0094] Blastocladiomycetes, such as Physoderma maydis;
[0095] [0095] Mucoromycetes, such as Choanephora cucurbitarum; Mucor spp .; Rhizopus arrhizus; as well as diseases caused by other species and genera closely related to those listed above.
[0096] [0096] In addition to their fungicidal activity, the compositions may also have activity against bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Strptomyces scabies and other related species as well as certain protozoa.
[0097] [0097] The composition according to the invention is particularly effective against phytopathogenic fungi belonging to the following classes: Ascomycetes (eg, Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula); Basidiomycetes (eg, from the genus Hemileia, Rhizoctonia, Phakopsora, Puccinia, Ustilago, Tilletia); Imperfect fungi (also known as Deuteromycetes; eg, Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Pyricularia and Pseudocercosporella); Oomycetes (eg, Phytophthora, Peronospora, Pseudoperonospora, Albugo, Bremia, Pythium, Pseudosclerospora, Plasmopara).
[0098] Useful plant cultures in which the composition according to the invention can be used include perennial and annual crops, such as berries plants, 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; grams, for example Bermuda grass, blue grass, agrostis, centipede grass, fescue,
[0099] [0099] Cultures are to be understood as those that occur naturally, obtained by conventional breeding methods or obtained by genetic engineering. They include crops that contain the so-called resulting characteristics (eg improved storage stability, higher nutritional value and improved taste).
[00100] [00100] Cultures are to be understood as also including those cultures that have been made tolerant to herbicides such as bromoxynil or to classes of herbicides such as ALS, EPSPS, GS, HPPD and PPO inhibitors. An example of a culture that has been made tolerant to imidazolinones, e.g. ex. to imazamox, by conventional breeding methods is the summer canola Clearfieldo. Examples of crops that have been made tolerant to herbicides by genetic engineering methods include e.g. ex. glyphosate and glufosinate resistant maize varieties, commercially available under the trade names RoundupReady6, Herculex IO and LibertyLinko.
[00101] [00101] Cultures are also to be understood as those that are or have been naturally made resistant to harmful insects. This includes plants transformed by the use of recombinant DNA techniques, for example, to be able to synthesize one or more toxins with selective action, such as those known, for example, of toxin-producing bacteria. Examples of toxins that can be expressed include G3-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins from nematode-colonizing bacteria and toxins produced by scorpions, arachnids, wasps and fungi.
[00102] [00102] An example of a culture that has been modified to express Bacillus thuringiensis toxin is the most Bt KnockOutO (Syngenta Seeds). An example of a culture comprising more than one gene that encodes insecticidal resistance and thus expresses more than one toxin is VipCot & (Syngenta Seeds). Crops or their seed material can also be resistant to various types of pests (so-called stacked transgenic events when created by genetic modification). For example, a plant may have the ability to express an insecticidal protein, while at the same time it is tolerant to herbicides, for example Herculex IO (Dow AgroSciences, Pioneer Hi-Bred International).
[00103] [00103] The compounds of formula (II), in particular compounds Q.001, Q.002, 90.003, Q.004, 90.005, Q.006, 9.007,
[00104] [00104] The use of compounds of formula (I), in particular compounds 0.001, 0.002, 90.003, Q.004, Q.005, Q.006, 9.007,
[00105] [00105] In particular, given the teachings in the cited patent publications (above), it is expected that compounds of formula (I), in particular compounds Q.001,
[00106] [00106] Thus, here is provided a method of controlling pest and / or phytopathogenic fungi (such as Phakopsora pachyrhizi) in genetically modified soy crops (such as transgenic soy plants comprising the MON87701 event; see US Patent No. 8,049,071 and orders and related patents, as well as WO 2014/170327 A1, paragraph [008] with reference to Intacta soybean RR2 PRO '""), which includes the application to the crops of genetically modified soybeans of compounds of formula (I), especially preferred compounds Q.001, Q.002, Q.003, Q.004,
[00107] [00107] Other preferred examples of compositions according to the invention are as follows (where the term "TO1" designates: "a compound, or a salt, enantiomer, tautomer or N-oxide thereof, selected from Q.001 , Q.002, Q.003
[00108] [00108] The compositions of the present invention, including all of the modalities disclosed above and their preferred examples, can be mixed with one or more additional pesticides including fungicides, insecticides, nematocides, bactericides, acaricides, growth regulators, chemosterilizers, semi-chemicals, repellents, attractants, pheromones, food stimulants or other additional biologically active compounds to form a multi-component pesticide, giving an even broader spectrum of agricultural protection.
[00109] [00109] Examples of such agricultural protectors with which the composition of the present invention can be formulated are:
[00110] [00110] Fungicides such as etridiazole, fluazinam, benalaxyl, benalaxyl-M (chiralaxyl), furalaxyl, metalaxyl, metalaxyl-M (mefenoxam), dodicin, N '- (2,5-Dimethyl-4-phenoxy-phenyl) -N -ethyl-N-methyl-formamidine, N '- [4- (4,5-Dichloro-thiazol-2-yloxy) -2,5-dimethyl-phenyl] -N-ethyl-N-methyl-formamidine, N' - [4 - [[3- [(4-chlorophenyl) methyl] -1,2,4-thiadiazole-5-11] oxy] -2,5-dimethyl-phenyl] -N-ethyl-N-methyl-formamidine , ethirimol, 3'-chloro-2-methoxy-N - [(3RS) -tetrahydro-2-oxofuran-3-yl] aceto-2 ', 6'-xylidide (clozilacone), cyprodinil, mepanipyrim, pyrimethanil, dithianone, aureofungin, blasticidin-S, biphenyl, chloroneb, dichlorane, hexachlorobenzene, quintozene, tecnazene, (TCNB), tolclofós-methyl, metrafenone, 2,6-dichloro-N- (4-trifluoromethylbenzyl) -benzamide, fluicolide , thioximide, flussulfamide, benomile, carbendazim, carbendazim hydrochloride, chlorphenazole, fuberidazole, thiabendazole, thiophanate-methyl, bentiavalicarb, clobentiazone, probenazole, acibenzolar, betoxazine, Ppiriofenon a (IKF-309), acibenzolar-S-methyl, pyribencarb (KIF-7767), butylamine, 3-iodo-2-propynyl n-butylcarbamate (TPBC), iodocarb (deisopropanyl butylcarbamate), isopropanyl butylcarbamate (iodocarb), picarbutrazox, polycarbamate, propamocarb, tolprocarb, 3- (difluoromethyl) -N- (7-fluoro-1, 1,3,3-tetramethyl-indan-4-yl) - 1-methyl-pyrazol-4-carboxamide, diclocimete, N - [(5-chloro-2-isopropyl-phenyl) methyl] -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-pyrazol-4-carboxamide, N-cyclopropyl-3- (di-fluoromethyl ) -5-fluoro-N - [(2-isopropylphenyl) methyl] -1-methyl-pyrazol-4-carboxamide, carpropamide, chlorothalonil, flumorfe, oxin-copper, cyoxoxanil, phenamacryl, cyazofamide,
[00111] [00111] Insecticides such as abamectin, acephate, acetamipride, starch (S-1955), avermectin, azadiractin, azinphos-methyl, bifenthrin, biphenazate, buprofezin, carbofuran, chart, chloranthranilprol (DPX-E2Y45, chlor-chlorapyrone, chlor-fluorine, chlor-fluorine, chlor-fluorine, chlor-fluorine, chlorine chlorpyrifos-methyl, chromafenozide, clothianidin, kiflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafentiuron, diazinone, dieldrin, dihydrofuran, dimlurururine, dihydrofuran, dimlurururine, dimlubururon, dimlurururine, dimlurururine, dimlururine etiprol, phenothiocarb, phenoxycarb, fenpropatrin, fenvalerate, fipronil, flonicamide, flubendiamide, flucitrinate, tau- fluvalinate, flufenerime (UR-50701), flufenoxurone, fonofós, halofenozida, hexaflumurona, isofluidone, , metaldehyde, metamidophos, methidathione, methomyl, methoprene, methoxychlor, metoflutrin, monocrotophos, methoxyfenozide, nitenp irame, nithiazine, novalurona, noviflumurona (XDE-007), oxamila, parathion, parationa- methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, pymetrozine, pirafluprol, pyrethrin, piridalila, pirifluquinazona, pyriprole, pyriproxyfen , rotenone, rianodine, espinetorame, spinosad, spirodiclofen, spiromesifene (BSN 2060), spirotetramate, sulprofós, tebufenozida, teflubenzurone, teflutrina, terbufós, tetrachlorvinfós, tiacloprida,
[00112] [00112] Bactericides such as streptomycin;
[00113] [00113] Acaricides such as amitraz, quinomethionate, chlorobenzylate, cyienopirafen, cyiexatin, dicofol dienochlor, ethoxazole, phenazaquin, fenbutatin oxide, fenpropatrin, fenpyroxy, hexitiazox, propargite, pyridabene and tebufenpirate; and
[00114] [00114] Biological agents such as Bacillus thuringiensis, Bacillus thuringiensis delta-endotoxin baculovirus, and entomopathogenic bacteria, viruses and fungi.
[00115] [00115] Other examples of mixing compositions are as follows (where the term "TQ" designates: a compound, or a salt thereof, enantiomer, tautomer or N-oxide, selected from Q.001, Q.002, Q.003, Q.004, Q.005, Q.006,
[00116] [00116] 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 previously for the particular compound; for example, the compound "abamectin" is described under the entry number (1). When “[CCN]” is added above to the particular compound, the compound in question is included in the “Compendium of Pesticide Common Names”, which is accessible on the Internet [A. Wood; Compendium of Pesticide Common Names, Copyright O 1995-2004]; for example, the compound “acetoprol” is described under the Internet address http://www.alanwood.net/pesticides/acetoprole.html
[00117] [00117] Most of the active ingredients described above are referred to above 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 this case the name IUPAC is used, the name IUPAC / Chemical
[00118] [00118] The active ingredient mixture of the compounds of formula (1) selected from Table OQ (above) with active ingredients described above comprises a compound selected from Table Q (above) and an active ingredient as described above, preferably in a ratio mixing ratio from 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, especially 5: 1 and 1: 5, with a special 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.
[00119] [00119] In a preferred embodiment, the compositions according to the invention comprise a weight ratio of component (A) to component (B) in the range of 30: 1 to 1:40.
[00120] [00120] Preferred field rates of the mixing partner: compound of formula (I) from Table Q, and also the preferred ratios of the mixing partner: a compound of formula (I) from Table Q, are provided in the Table below for certain preferred individual mixing partners:
[00121] [00121] Mixtures as described above can be used in a method to control 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 pests. human or animal body by surgery or therapy and diagnostic methods practiced on the human or animal body.
[00122] [00122] Mixtures comprising a compound of formula (1) selected from Table Q (above) and one or more active ingredients, as described above, can be applied, for example, in a simple "ready-mix" form, in a combined spray mixture prepared from separate formulations of the components of the individual active ingredients, such as a "tank mixture", and in a combined use of the individual active ingredients when applied in a sequential manner, ie one after the other in a relatively short period of time, such as a few hours or days. The order of application of the compounds of formula (1) selected from Table Q (above) and of the active ingredients as described above is not essential to the realization of the present invention.
[00123] [00123] The compositions of the present invention can also be used in enhancing cultures.
[00124] [00124] According to the present invention, "crop intensification" means an improvement in plant vigor, an improvement in plant quality, improved tolerance to stress factors and / or improved plant resource efficiency.
[00125] [00125] According to the present invention, an "improvement in plant vigor" means that certain characteristics are improved qualitatively or quantitatively compared to the same characteristic in a control plant that was grown under the same conditions in the absence of the method of invention. Such characteristics include, but are not limited to, early and / or improved germination, improved emergence, the ability to use fewer seeds, increased root growth, a more developed root system, increased root nodulation, increased sprout growth, increased tillering, stronger shoots, more productive shoots, increased or improved ability to remain upright, less inclination
[00126] [00126] According to the present invention, an "improvement in plant quality" means that certain traits are improved qualitatively or quantitatively compared to the same trait in a control plant that was grown under the same conditions in the absence of the method of invention. Such characteristics include, but are not limited to, improved visual appearance of the plant, reduced ethylene (reduced production and / or inhibition of reception), improved quality of collected material, e.g. eg, seeds, fruits, leaves, vegetables (such an improved quality may manifest itself as an improved visual appearance of the collected material), improved carbohydrate content (eg, increased amounts of sugar and / or starch, improved ratio of sugars to acids, reduction of reducing sugars, increased rate of sugar development), improved protein content, improved oil content and composition, improved nutritional value, reduction in antinutritional compounds, improved organoleptic properties (eg, improved taste) and / or improved health benefits for the consumer (eg, increased levels of vitamins and antioxidants), improved post-collection characteristics (eg, enhanced shelf life and / or storage stability, easier processability, more extraction easy to compost), more homogeneous crop development (eg, germination, flowering and / or production of synchronized plant fruits), and / or improved quality of seeds (p. for use in subsequent seasons). A plant with improved quality can have an increase in any of the above mentioned characteristics or any combination of two or more of the above mentioned characteristics.
[00127] [00127] According to the present invention, an "improved tolerance to stress factors" means that certain characteristics are improved qualitatively or quantitatively compared to the same characteristic in a control plant that was grown under the same conditions in the absence of the method of the invention. Such characteristics include, but are not limited to, an increased tolerance and / or resistance to abiotic stress factors that cause suboptimal growth conditions, such as drought (eg, any stress that leads to an absence of water content in plants, a lack of potential for water uptake or a reduction in water supply to plants), exposure to cold, heat exposure, osmotic stress, UV stress, waterlogging, increased salinity (eg in soil) , increased exposure to minerals, exposure to ozone, high exposure to light and / or limited availability of nutrients (eg, nutrients containing nitrogen and / or phosphorus). A plant with improved tolerance to stress factors may experience an increase in any of the above mentioned characteristics or any combination of two or more of the above mentioned characteristics. In the case of stress due to drought and nutrients, such improved tolerances may be due, for example, to the more efficient capture, use or retention of water and nutrients.
[00128] [00128] According to the present invention, an "improved resource-use efficiency" means that plants are able to grow more effectively using given resource levels compared to the growth of control plants that are grown under the same conditions in the absence of the inventive method. In particular, resources include, but are not limited to, fertilizer (such as nitrogen, phosphorus, potassium, micronutrients), light and water. A plant with improved resource efficiency may have a use improved from any of the above features or any combination of two or more of the above features.
[00129] [00129] Other intensifications of the crops of the present invention include a decrease in plant height, or reduction in tillering, which are beneficial characteristics in crops or conditions where it is desirable to have less biomass and less shoots.
[00130] [00130] Any one, or all, of the above crop intensifications can lead to improved yield by improvement, e.g. eg, plant physiology, plant growth and development and / or plant architecture. In the context of the present invention, "yield" includes, but is not limited to: (i) an increase in biomass production, grain yield, starch content, oil content and / or protein content, which may result from (a) an increase in the amount produced by the plant per se or (b) an improved ability to harvest plant material, (ii) an improvement in the composition of the harvested material (eg, better acid-sugar ratios, better oil composition , greater nutritional value, reduction of anti-nutritional compounds, greater benefits for the health of the consumer) and / or (iii) greater capacity or facility to harvest the culture, better processability of the culture and / or better storage stability / shelf life. Increased yield of an agricultural plant means that, when it is possible to make a quantitative measurement, the yield of a product of the respective plant is increased by a measurable amount in relation to the yield of the same product of the plant produced under the same conditions, but without application of the present invention. According to the present invention, it is preferred that the yield is increased by at least 0.5%, more preferably at least 1%, even more preferably at least 2%, even more preferably at least 4%, preferably 5% or even more.
[00131] [00131] Any, or all, of the crop intensifications above may also lead to improved land use, that is, land that was previously unavailable or was suboptimal for cultivation may become available. For example, it may be possible to grow plants that exhibit an increased ability to survive in drought conditions in areas of suboptimal rainfall, e.g. eg, perhaps on the edge of a desert or even in the desert itself.
[00132] [00132] In one aspect of the present invention, crop enhancements are made in the substantial absence of pest and / or disease pressure and / or abiotic stress. In a further aspect of the present invention, improvements in plant vigor, stress tolerance, quality and / or yield are made in the substantial absence of pest and / or disease pressure. For example, pests and / or diseases can be controlled by a pesticidal treatment that is applied before, or at the same time as, the method of the present invention. In a still further aspect of the present invention, improvements in vigor, stress tolerance, quality and / or yield of plants are made in the absence of pressure from pests and / or diseases. In an additional modality, improvements in plant vigor, quality and / or yield are made in the absence, or substantial absence, of abiotic stress.
[00133] [00133] The compositions of the present invention can also be used in the field of protection of storage goods against attack by fungi. According to the present invention, the term "storage goods" is understood to denote natural substances of plant and / or animal origin and their processed forms, which have been removed from the natural life cycle and for which long-term protection is desirable. deadline. Storage goods of plant origin, such as plants or parts of them, for example, stems, leaves, tubers, seeds, fruits or grains, can be protected as freshly collected or in processed form, such as pre-dried, moistened, comminuted, ground, pressed or roasted. Also included in the definition of storage goods is wood, either in the form of raw wood, such as construction timber, electricity poles and barriers, or in the form of finished articles, such as furniture or objects made of wood. Storage goods of animal origin are fur, leather, fur, fur and the like. The composition according to the present invention can prevent disadvantageous effects such as degradation, discoloration or mold. Preferably, "storage goods" are understood to denote natural substances of vegetable origin and / or their processed forms, more preferably fruits and their processed forms, such as pomoideas, stone fruits, soft fruits and citrus fruits and their processed forms. In another preferred embodiment of the invention, "storage goods" are understood to denote wood.
[00134] [00134] Therefore, an additional aspect of the present invention is a method of protecting storage goods, which comprises applying to storage goods a composition according to the invention.
[00135] [00135] The composition of the present invention can also be used in the area of protection of technical material against fungal attack. According to the present invention, the term "technical material" includes paper; carpets; constructions; cooling and heating systems; wall panels; air conditioning and ventilation systems and the like;
[00136] [00136] The compositions according to the invention are generally formulated in various ways using formulation aids, such as vehicles, solvents and surfactants. The formulations can be in various physical forms, eg in the form of dust powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent granules, emulsifiable concentrates, microemulsifiable concentrates, oil-in-emulsions water, flowable oils, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as a vehicle), impregnated polymer films or other known forms, eg from the "Manual on Development and Use of FAO and WHO Specifications for Pesticides", United Nations, First Edition, Second Review (2010). Such formulations can be used directly or diluted before use. Dilutions can be made, for example, with water, in liquid fertilizers, micronutrients, biological organisms, oil or solvents.
[00137] [00137] Formulations can be prepared p. ex. mixing the active ingredient with the formulation aids in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surfactants or combinations thereof.
[00138] [00138] The active ingredients can also be contained in very thin microcapsules. The microcapsules contain the active ingredients in a porous vehicle. This allows the active ingredients to be released into the environment in controlled quantities (eg slow release). Microcapsules usually have a diameter of 0.1 to 500 microns. They contain active ingredients in an amount of about 25 to 95% by weight of the weight of the capsule. The active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion, or in the form of a suitable solution. Encapsulation membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene / butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers which are known to the skilled person in the technique. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
[00139] [00139] Formulation adjuvants which are suitable for the preparation of formulations according to the invention are known per se. Liquid vehicles can be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, acetic acid alkyl esters, diacetonic alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycolbutyl ether, diethylene glycol ether, diethylene glycol ether, methylene glycol, methylene glycol, ether dimethylsulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, alpha-pinene , d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, h exadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, iso-octane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl islamethylate, methylisobutane, methylisobutane, methylisobutane , methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichlorethylene, perchlorethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol and higher molecular weight alcohols, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone and the like.
[00140] [00140] Suitable solid vehicles are, for example, talc, titanium dioxide, pyrophyllite clay, silica, atapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cotton seed husks, wheat flour , soy flour, pumice, wood flour, crushed nut shells, lignin and similar substances.
[00141] [00141] A large number of surfactants can be advantageously used in solid and liquid formulations, especially those formulations that can be diluted with a vehicle before use. Surfactants can be anionic, cationic, nonionic or polymeric, and can be used as emulsifiers, wetting agents or suspending agents, or for other purposes. Typical surfactant substances include, for example, alkyl sulfate salts, such as diethanolammonium lauryl sulfate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol / alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol / alkylene oxide addition products, such as tridecyl alcohol ethoxylate; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as di (2-ethyl-
[00142] [00142] Additional adjuvants that can be used in pesticidal formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, antifoams, complexing agents, neutralizing substances or pH modifiers and buffers, corrosion inhibitors, fragrances, wetting agents, adhesion enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze, microbicides and liquid and solid fertilizers.
[00143] [00143] The formulations according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils, or mixtures of such oils and oil derivatives. The amount of oil additive in the formulation according to the invention is generally 0.01 to 10%, based on the mixture to be applied. For example, the oil additive can be added to a spray tank at the desired concentration after a spray mixture has been prepared. Preferred oil additives comprise mineral oils or a vegetable oil, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of vegetable oils, for example methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially methyl derivatives of C12-C18 fatty acids, for example methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives are known from the "Compendium of Herbicide Adjuvants", 10th Edition, Southern Illinois University, 2010.
[00144] [00144] The formulations generally comprise from 0.1 to 99% by weight, especially from 0.1 to 95% by weight, of compounds of formulas (1) and (II) and from 1 to 99.9% by weight of a formulation aid which preferably includes from 0 to 25% by weight of a surfactant. Although commercial products can preferably be formulated as concentrates, the end user will normally use diluted formulations.
[00145] [00145] Application rates vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions and other factors controlled by the method of application, the application time and the target culture. As a general guideline, the compounds can be applied at a rate of 1 to 2000 L / ha, especially from 10 to 1000 L / ha.
[00146] [00146] Preferred formulations can have the following compositions (% by weight):
[00147] [00147] The combination is carefully mixed with the adjuvants and the mixture is carefully ground in a suitable mill, creating wettable powders that can be diluted with water to give suspensions of the desired concentration. a) b) c) Dry seed treatment powders. . 25% 50% 75% active ingredients 5% 5% 5% light mineral oil, 5% 5% highly dispersed silicic acid. 65% 40% Kaolin Talc
[00148] [00148] The combination is carefully mixed with the adjuvants and the mixture is carefully ground in a suitable mill, giving rise to powders that can be used directly for seed treatment. | concentrate emisisible - - RD) | | 145 mons of etizenoy oxide - | | 2 mol of ethylene oxide)
[00149] [00149] Emulsions of any required dilution can be obtained, which can be used to protect plants, from this concentrate by dilution with water. | earo eso | | | [eai and as | | [filling mining bee)
[00150] [00150] Ready-to-use powders are obtained by mixing the combination with the vehicle and crushing the mixture in a suitable mill. Such powders can also be used for dry seed coatings.
[00151] [00151] The combination is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a draft. Coated granules | 8% active ingredients | 3% polyethylene glycol (molecular weight 200) 89% Kaolin
[00152] [00152] The finely crushed combination is uniformly applied, in a mixer, to kaolin moistened with polyethylene glycol. in this way, coated, non-dusty granules are obtained. Concentrate in suspension 40% active ingredients. 10% propylene glycol 6% nonylphenol polyethylene glycol ether (15 mol of ethylene oxide), 10% Sodium lignosulfonate 1% carboxymethylcellulose | 1% silicone oil (in the form of an emulsion at 75% in water) At 32% water
[00153] [00153] The finely crushed combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by diluting 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.
[00154] [00154] The finely crushed combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by diluting 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.
[00155] [00155] 28 parts of the combination 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 achieved. To this emulsion, a mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water is added. The mixture is stirred until the polymerization reaction is complete. 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. The resulting formulation is applied to the seeds as an aqueous suspension in an apparatus suitable for this purpose.
[00156] [00156] In general, the weight ratio of component (A) to component (B) is 2000: 1 to 1: 1000. A non-limiting example of such weight ratios is a compound of formula (1): compound of component (B) 10: 1. The weight ratio of component (A) to component (B) is preferably 100: 1 to 1: 100; more preferably from 20: 1 to 1:50.
[00157] [00157] The composition comprising the compound of formula (I) and the compound of formula (II) can have a synergistic effect. This occurs whenever the action of a combination of active ingredients is greater than the sum of the actions of the individual components. The action to be expected AND for a given combination of active ingredients obeys the so-called COLBY formula and can be calculated as follows (COLBY, SR “Calculating synergistic and antagonistic responses of herbicide combination”. Weeds, Vol. 15, pages 20-22; 1967): ppm = milligrams of active ingredient (= ai) per liter of spray mixture X =% action by active ingredient A) using p ppm active ingredient Y =% action by active ingredient B) using q ppm of active ingredient.
[00158] [00158] According to COLBY, the expected (additive) action of active ingredients A) + B) using ptq ppm of active ingredient is: Esx + y AX 100
[00159] [00159] If the action actually observed (O) is greater than the action expected (E), then the action of the combination is superadditive, that is, there is a synergistic effect. In mathematical terms, synergy corresponds to a positive value for the difference of (O-E). In the case of adding activities (expected activity) purely complementary, the referred difference (O-E) is zero. A negative value of the referred difference (O-E) signals a loss of activity compared to the expected activity.
[00160] [00160] However, in addition to the actual synergistic action with respect to the fungicidal activity, the composition according to the invention can also have additional surprising advantageous properties. Examples of such advantageous properties that can be mentioned are: more advantageous degradability; improved toxicological and / or ecotoxicological behavior; or improved characteristics of useful plants including: emergence, crop yields, more developed root system, increased tillering, increased plant height, greater leaf depth, less dead basal leaves, stronger shoots, greener leaf color, less necessary fertilizers, less seeds needed, more productive shoots, early flowering, early grain maturity, less plant inclination (lodging), increased shoot growth, improved plant vigor and early germination.
[00161] [00161] The composition according to the invention can be applied to phytopathogenic microorganisms, to useful plants, to their location, to their propagating material, storage goods or technical materials threatened by attack by microorganisms.
[00162] [00162] The composition according to the invention can be applied before, or after, the infection of useful plants, their propagating material, storage goods or technical materials by microorganisms.
[00163] [00163] The amount of a composition according to the invention to be applied will depend on several factors, such as the compounds employed; the object of the treatment, such as, for example, plants, soil or seeds; the type of treatment, such as, for example, spraying, dusting or covering seed; the purpose of the treatment, such as, for example, prophylactic or therapeutic; the type of fungi to be controlled or the time of application.
[00164] [00164] When applied to useful plants, component (A) is typically applied at a rate of 5 to 2000 g a.i./ha, particularly 10 to 1000 g a.i./ha, p. e.g., 50,
[00165] [00165] In agricultural practice, the rates of application of the composition according to the invention depend on the type of effect desired and, typically, vary from 20 to 4000 g of the total composition per hectare.
[00166] [00166] When the composition according to the invention is used for seed treatment, rates of 0.001 to 50 g of a compound of component (A) per kg of seed are generally sufficient, preferably from 0.01 to 10 g per kg of seed, and 0.001 to 50 g of a compound of component (B) per kg of seed, preferably from 0.01 to 10 g per kg of seed.
[00167] [00167] Using techniques described above and below, and also in WO 08/101682 (pp. 22-33) and WO 12/146125 (pp. 370-378), in conjunction with other techniques generally known to the person skilled in the art, compounds of formula (I) can be prepared.
[00168] [00168] N-bromosuccinimide (1.28 g, 7.29 mmol) was added portion-by-portion to an ice-cold solution
[00169] [00169] 1 H NMR (400 MHz, CDCl 3): at 7.17 (s, 1H), 6.27 (s, 1H), 3.82 (s, 3H), 3.53-3.73 ( bs, 2H), 2.08 (s, 3H).
[00170] [00170] To a suspension of 4-bromo-5-methoxy-2-methyl-aniline (1.4 g, 6.48 mmol) and p-toluenesulfonic acid (0.05 g, 0.32 mmol) in toluene ( 13 ml) N- (dimethoxymethyl) -N-methyl-ethanamine (1.3 g, 9.7 mmol) was added at room temperature. The resulting clear solution was heated to 50 ° C and stirred for 24 h at this temperature. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate, washed with aqueous NaHCO3, brine and dried with MgSOs. The solids were removed by filtration and the volatiles were removed under vacuum. The residue was purified by flash chromatography on silica gel to give the title compound as a light yellow liquid.
[00171] [00171] 1 H NMR (400 MHz, CDCl 3): 5.40 (s 1, 1H), 7.26 (s, 1H), 6.33 (s, 1H), 3.85 (s, 3H ), 3.34 (s 1, 2H) 3.00 (s, 3H), 2.16 (s, 3H), 1.22 (t, 3H).
[00172] [00172] A solution of N '- (4-bromo-5-methoxy-2-methyl-phenyl) -N-ethyl-N-methyl-formamidine (0.10 g, 0.35 mmol) in dry tetrahydrofuran (3.5 mL) under N> atmosphere; it was cooled to -78 ° C and tert-butyl lithium (1.5 M in pentanes, 0.49 mL, 0.74 mmol) was added slowly. The reaction was aged for 5 min at -78 ° C and then 1-phenylethanone (0.044 9g, 0.37 mmol) was added dropwise. The cooling bath was removed, the reaction was allowed to warm to room temperature and stirred for a further min. NaHCO was added; aqueous and the mixture was extracted with EtOAc. The organic layer was washed with brine, dried over MgSOs, filtered and concentrated in vacuo. The residue was purified by flash chromatography on silica gel to give the title compound as a white solid.
[00173] [00173] 1 H NMR (400 MHz, CDCl 3): 5 7.41 (s 1, 1H), 7.28-7.34 (m, 2H), 7.12-7.25 (m, 4H) , 6.32 (s, 1H), 4.64 (s, 1H), 3.51 (s, 3H), 3.20-3.47 (s 1, 2H), 3.00 (s, 3H) , 2.24 (s, 3H), 1.80 (s, 3H), 1.21 (t, 3H).
[00174] [00174] A solution of N '- (4-bromo-5-methoxy-2-methyl-phenyl) -N-ethyl-N-methyl-formamidine (2.0 g, 7.01 mmol) in dry tetrahydrofuran (3.5 mL) under No. atmosphere) was added dropwise to a suspension of LiCl (0.33 q, 7.71 mmol) and Mg shavings (0.26 g, 7.02 mmol) in dry tetrahydrofuran (3.5 mL) at a temperature between 20 "ºC and 40" Cc (temperature controlled by the rate of addition). After the addition was complete, the reaction was aged for 1 h at 40 ºC and then the mixture was then cooled to O “ºC. N-methoxy-N, 2-dimethyl-propanamide (1.01 g, 7.33 mmol) was added dropwise and the reaction mixture was gradually heated to RT over 1 h. Aqueous NH NHCl solution was added and the mixture was extracted with EtOAc. The organic layer was washed with water, brine, dried over MgSO4, filtered and concentrated in vacuo. The residue was purified by flash chromatography on silica gel to give the title compound as a light yellow oil.
[00175] [00175] 1 H NMR (400 MHz, CDCl 3) 5 7.47 (s 1, 2H), 6.30 (s, 1H), 3.85 (s, 3H), 3.25 - 3.60 ( m, 3H), 3.02 (s, 3H) 2.18 (s, 3H), 1.59 (s, 1H), 1.23 (t, 3H), 1.13 (d, 6H) b) Preparation of N-ethyl-N '- [4- [1-hydroxy-2-methyl-l1- (trifluoromethyl) propyl] -5-methoxy-2-methyl-phenyl] -N-methyl-formamidine
[00176] [00176] Trimethyl (trifluoromethyl) silane (0.26 g, 1.81 mmol) was added dropwise to a solution of N-ethyl-N '- [5-methoxy-2-methyl-4- ( 2-methylpropanoyl) phenyl] -N-methyl-formamidine (0.50 g, 1.81 mmol) and CsF (0.03 g, 0.18 mmol) in toluene (9 mL) at 40 ҼC. The resulting mixture was aged for 3 h at 40 ҼC, a second portion of trimethyl (trifluoromethyl) silane (0.13 g, 0.91 mmol) was then added and the reaction was stirred for another 30 min before being concentrated in vacuo even a brown oil.
[00177] [00177] This residue was extracted in methanol (7 mL), treated with potassium carbonate (0.37 g, 2.71 mmol) and aq. (2 M, 3 drops), heated to 40 ºC and stirred for 24 h at this temperature. An aqueous solution of NaHCO was then added; and the emulsion was extracted with EtOAc. The organic layer was washed with water, brine, dried over MgSOs, filtered and concentrated in vacuo. The residue was purified by flash chromatography on silica gel to give the title compound as a light brown solid (mp 57-59 ° C).
[00178] [00178] * H NMR (400 MHz, CDCl3) 5 7.47 (s 1, 1H), 7.07 (s, 1H), 6.56 (s 1, 1H), 6.40 (s, 1H ), 3.90 (s, 3H), 3.22 - 3.66 (m, 2H), 3.03 (s, 3H), 2.46-2.66 (m, 1H), 2.22 ( s, 3H), 1.25 (t, 3H), 1.16 (d, 3H), 0.87 (d, 3H).
[00179] [00179] Bromosuccinimide No. (1.28 9, 7.29 mmol) was added portion-by-portion to an ice-cooled (0-5 ° C) solution of 5-methoxy-2-methyl-aniline (1.0 g, 7.29 mmol) in CHCl; (15 mL). The resulting solution was stirred for 60 minutes at 0 ºC, warmed to room temperature and diluted with CH; Cl; 7. The mixture was washed with NaHCO; aqueous (+ 2 ml NazS20: 3 solution), brine and dried over MgSO .. The solids were removed by filtration and the volatiles were removed under vacuum. The residue was purified by flash chromatography on silica gel to give the title compound as an off-white solid.
[00180] [00180] 1 H NMR (400 MHz, CDCl 3): 5 7.17 (s, 1H), 6.27 (s, 1H), 3.82 (s, 3H), 3.53-3.73 ( s 1, 2H), 2.08 (s 3H).
[00181] [00181] To a suspension of 4-bromo-5-methoxy-2-methyl-aniline (1.4 g, 6.48 mmol) and p-toluenesulfonic acid (0.05 g, 0.32 mmol) in toluene ( 13 ml) N- (dimethoxymethyl) -N-methyl-ethanamine (1.3 g9, 9.7 mmol) was added at room temperature. The resulting clear solution was heated to 50 ° C and stirred for 24 h at this temperature. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate, washed with aqueous NaHCO3, brine and dried with MgSOs. The solids were removed by filtration and the volatiles were removed under vacuum. The residue was purified by flash chromatography on silica gel to give the title compound as a light yellow liquid.
[00182] [00182] 1 H NMR (400 MHz, CDCl 3): 5.40 (s 1, 1H), 7.26 (s, 1H), 6.33 (s, 1H), 3.85 (s, 3H ), 3.34 (s 1, 2H) 3.00 (s, 3H), 2.16 (s, 3H), 1.22 (t, 3H).
[00183] [00183] A solution of N '- (4-bromo-5-methoxy-2-methyl-phenyl) -N-ethyl-N-methyl-formamidine (0.94 gq, 3.30 mmol) in THF was cooled (7 mL) under inert atmosphere to -78 ºC and dropwise (2.5 M in hexanes, 2.5 mL, 3.96 mmol) was added. The resulting solution was aged for 30 min at -78 ºC, then 2,2,2-ethyl trifluoroacetate (1.40 g, 9.89 mmol) was added, the flask was removed from the cooling bath and allowed to reach at room temperature. The mixture was inactivated with aq. and extracted with ethyl acetate. The organic layer was washed with brine, dried over MgSOs, filtered and concentrated in vacuo to a yellow oil. Purification by flash chromatography on silica gel to give the title compound as a light yellow solid.
[00184] [00184] 1 H NMR (400 MHz, CDCl 3): 5 7.55 (s, 1H), 7.36-7.54 (m, 1H), 6.32 (s, 1H), 3.89 ( s, 3H), 3.27-3.64 (mM, 2H), 3.05 (s, 3H), 2.20 (s, 3H), 1.16-1.35 (m, 3H).
[00185] [00185] Trimethylsulfonium iodide (0.52 g, 2.48 mmol) was added in small portions to an ice-cold suspension of sodium hydride (60% in oil, 0.11 g, 2.48 mmol) in tetrahydrofuran (8 ml) and dimethyl sulfoxide (6 ml). The cooling bath was removed and the mixture was stirred for 30 min at room temperature. A solution of N-ethyl-N '- [5-methoxy-2-methyl-4- (2,2,2-trifluoroacetyl) phenyl] -N-methyl-formamidine (0.50 g, 1.65 mmol) in tetrahydrofuran (5 mL) and the reaction was stirred at room temperature until HPLC indicated total conversion of the starting material. The mixture was cooled with an ice bath, carefully inactivated with aq. of NH'Cl and was extracted with ethyl acetate. The organic layer was washed with brine, dried over MgSOs, filtered and concentrated in vacuo to a light brown solid which was purified by flash chromatography on silica gel to give the title compound as a light brown solid.
[00186] [00186] 1 H NMR (400 MHz, CDCl 3): 5 7.43 (s 1, 1H), 7.20 (s, 1H), 6.31 (s, 1H), 3.81 (s, 3H ), 3.40 (d, 1H), 3.15- 3.66 (m, 2H), 3.00 (s, 3H), 2.95-2.93 (m, 1H), 2.18 ( s, 3H), 1.21 (t, 3H).
[00187] [00187] 2-Methylpropan-1-ol (0.11 g, 1.52 mmol) was added slowly to a suspension of sodium hydride (60%, 0.04 g, 1.0 mmol) in DMF (1 mL) at 0 ° C and the mixture was aged for 5 min at 0 ° C. A solution of N-ethyl-N '- [5-methoxy-2-methyl-4- [2- (trifluoromethyl) oxiran- 2-11] phenyl] -N-methyl-formamidine (0.20 g, 0.51 mmol) in DMF (1 mL), the resulting solution was heated to 65 ° C and stirred at this temperature until HPLC indicated total conversion of the starting material. The reaction was cooled to room temperature, diluted with aq. NHJKCl and extracted with ethyl acetate. The organic layer was washed with brine, dried over MgSOs, filtered and concentrated in vacuo to a brown oil. Purification by flash chromatography on silica gel to give the title compound as a light yellow liquid.
[00188] [00188] 1 H NMR (400 MHz, CDCl 3; -d) 5 7.43 (s 1, 1H), 7.31 (s, 1H), 6.34 (s, 1H), 5.49 (s , 1H), 4.13 (d, 1H), 3.89 (d, 1H), 3.83 (s, 3H), 3.17-3.59 (m, 4H), 3.00 (s, 3H), 2.19 (s, 3H), 1.81 - 1.98 (m, 1H), 1.21 (t, 3H), 0.88 (dd, 6H).
[00189] [00189] Step 1. Preparation of N-ethoxypropan-2-imine
[00190] [00190] To a suspension of sodium hydroxide (9.44 g, 236 mmol) in DMSO (40 mL) was added propan-2-one oxime (15.0 9 g, 205 mmol) at 23 ° C. The reaction mixture was stirred for 5 min at this temperature and bromoethane (22.8 ml, 308 mmol) was added dropwise over approx. 15 min After the addition was complete, the reaction was heated to 60 “ºC and aged for 60 min at this temperature. The mixture was cooled to 20 ºC, diluted with water and light petroleum. The layers were separated, the organic layer was washed with brine, dried over MgSOs and filtered. Fractional distillation at atmospheric pressure gave the title compound as a colorless liquid, b.p. 90 “ºC.
[00191] [00191] 1H NMR (400 MHz, DMSO) 3.96 (q, 2H), 1.79 (s, 3H), 1.77 (s, 3H), 1.16 (t, 3H).
[00192] [00192] Step 2. Preparation of N '- [4- [3-ethoxy-imino-1-hydroxy-1- (trifluoromethyl) butyl] -5-methoxy-2-methyl-phenyl] -N- ethyl-N- methyl-formamidine.
[00193] [00193] A solution of N-ethoxypropan-2-imine (4.39, 39 mmol) in dry oxolane (10 mL) was added dropwise to lithium diisopropylamide (0.8 M solution in oxolane , 44 mL, 39 mmol) at -78 ° C and the reaction was aged for 60 min at this temperature. Then, a solution of N-ethyl-N '- [5-methoxy-2-methyl-4- (2,2,2-trifluoroacetyl) phenyl] -N-methyl-formamidine (7.8 g, 26 mmol) in dry oxolane (30 mL). The reaction was stirred for 10 min at - 78 ºC, the cooling bath was removed and the reaction heated to 20 ºC. NaHCO was added; (saturated) and the mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried over MgSOs, filtered and concentrated in vacuo. The oily residue was purified by medium pressure chromatography on silica gel to give the title compound as a colorless oil.
[00194] [00194] 1 H NMR (400 MHz, CDCl 3) 7.43 (s, 1H) 7.15 (s, 1H), 6.39 (s, 1H), 6.13 (s, 1H), 4 , 08-4.17 (m, 2H), 3.88 (s, 3H), 3.83 (d, 1H), 3.22-3.63 (m, 2H), 3.02 (s, 3H ), 2.75 (d, 1H), 2.16 (s, 3H), 1.70 (s, 3H), 1.32 (t, 3H), 1.23 (t, 3H).
[00195] [00195] The compounds of formula (1) in Table Q 'were prepared using techniques analogous to those described above and / or common synthetic techniques generally known to the person skilled in the art, as well as those described in WO 12/146125 (pp. 370-378 ) and WO 08/101682 (pp. 22-33).
[00196] [00196] Method A:
[00197] [00197] The spectra were recorded on a Waters 10 Mass Spectrometer (ACQUITY UPLC) (single quadrupole mass spectrometer SQD, SQDII or Z2Q) equipped with an electrospray source
[00198] [00198] Method B:
[00199] [00199] The spectra were recorded on a Waters Mass Spectrometer (ACQUITY UPLC) (SQD, SQDII single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.0 kV, Cone: 30V, Extractor: 3.00 V, Source Temperature: 150 ºC, Desolvation Temperature: 400 ºC, Cone Gas Flow: 60 L / hour, Desolvation Gas Flow: 700 L / hour, Mass Range : 140 to 800 Da), DAD wavelength range (nm): 210 to 400, and a Waters UPLC Acquity: Solvent degasser, binary pump, heated column compartment and diode array detector. Column: UPLC HSS T3 from Waters, 1.8 um, 30 x 2.1 mm, Temp: 60 ºC, DAD wavelength range (nm): 210 to 500, Solvent Gradient: A = Water / Methanol 9 : 1, 0.1% formic acid, B = Acetonitrile + 0.1% formic acid, gradient: 0-100% B in 2.5 min; Flow (mL / min) 0.75 Biological examples for compounds of formula (TI):
[00200] [00200] Certain compositions of the invention can be distinguished from known compositions and compounds by virtue of being more effective at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates. low, if necessary, for example, 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm and / or 0.2 ppm. The use of "concentration / dilution factors" in biological tests to determine the intrinsic biological efficacy of bioactive molecules is known in the art.
[00201] [00201] Leaf segments of wheat cv. Kanzler were placed on agar in a multi-well plate (24-well format) and sprayed with the formulated test mixture compound or composition diluted in water. The leaf discs were inoculated by shaking plants infected with powdery mildew over the test plates, 1 day after application. The inoculated leaf discs were incubated at 20 ºC and 60% ur under a 24-hour dark light regime followed by 12 hours of light / 12 hours of darkness in an air-conditioned chamber, and the activity of a compound or mixture composition it was evaluated in the form of percentage control of the disease, compared to the absence of treatment, when an appropriate level of damage caused by the disease appears on untreated leaf segments of control (6 to 8 days after application).
[00202] [00202] The following compounds provided at least 200 ppm at least 80% disease control in this test compared to untreated leaf control discs under the same conditions, which exhibit extensive disease development:
[00203] [00203] 90,001, 9,002, 9,003, 90,004, 9,006, 9,007, 9,009,
[00204] [00204] Leaf segments of wheat cv. Kanzler were placed on agar in multi-well plates (24-well format) and sprayed with the formulated test mixture compound or composition diluted in water. The leaf discs were inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf segments were incubated at 19 ºC and 75% of ur under a light regime of 12 hours of light / 12 hours of darkness in an air-conditioned chamber, and the activity of a compound or mixture composition was evaluated as a percentage control of disease, compared to the lack of treatment, when an appropriate level of damage caused by the disease appears in untreated leaf control segments (7 - 9 days after application).
[00205] [00205] The following compounds provided at 200 ppm at least 80% disease control in this test compared to untreated leaf control discs under the same conditions, which exhibit extensive disease development:
[00206] [00206] 0.001, 9.002, 90.003, 90.004, 9.006, 90.007, 9.008,
[00207] [00207] Leaf segments of wheat cv. Kanzler are placed on agar in multi-well plates (24-well format). The leaf segments are inoculated with a spore suspension of the fungus. The plates were stored in the dark at 19 ºC and 75% ur. The formulated test mixture compound or composition diluted in water was applied 1 day after inoculation. The leaf segments were incubated at 19 ºC and 75% of ur under a 12-hour light / 12-hour dark regime in an air-conditioned chamber, and the activity of a compound or mixture composition was evaluated as percent disease control , compared with no treatment, when an appropriate level of damage caused by the disease appears in untreated leaf control segments (6 to 8 days after application).
[00208] [00208] The following compounds provided, at 200 ppm, at least 80% disease control in that test compared to untreated leaf control discs under the same conditions, which exhibit extensive disease development:
[00209] [00209] 9,001, 9,002, 9,003, 9,004, 9,006, 9,007, 9,008,
[00210] [00210] Soybean leaf discs are placed in agar water 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 75% of ur, the leaf discs are kept at 20 ºC with 12 h of light / day and 75% of ur. The activity of a compound is assessed as the percentage of disease control compared to the absence of treatment when an appropriate level of damage caused by the disease appears on untreated leaf control discs (12 - 14 days after application).
[00211] [00211] The following compounds gave at least 80% control of Phakopsora pachyrhizi at 200 ppm compared to an untreated control under the same conditions, which showed extensive disease development:
[00212] [00212] 90,001, 9,002, 90,003, 90,004, 90,005, 9,006, 9,007,
[00213] [00213] Leaf segments of wheat cv. Kanzler are placed on agar in a multi-well plate (24-well format) and sprayed with the formulated test mixture compound or composition diluted in water. Leaf discs are inoculated by shaking powdery mildew-infected plants over the test plates 1 day after application. The inoculated leaf discs are incubated at 20 ºC and 60% of ur under a light regime of 24 hours of darkness followed by 12 hours of light / 12 hours of darkness in an air-conditioned chamber, and the activity of a compound or mixture composition it is evaluated in the form of percentage control of the disease, compared to the absence of treatment, when an appropriate level of damage caused by the disease appears on untreated leaf control segments (6 to 8 days after application).
[00214] [00214] Conidia of the cryogenic storage fungus are directly mixed in nutrient broth (potato broth and PDB dextrose). After placing a solution (DMSO) of the test compound or composition in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 ° C and growth inhibition is determined photometrically 4-5 days after application.
[00215] [00215] Soybean leaf discs are placed in agar water in multi-well plates (24-well format) and sprayed with the formulated test mixture compound or composition 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 75% of ur, the leaf discs are kept at 20 ºC with 12 h of light / day and 75% of ur. The activity of a compound or mixture composition is assessed as a percentage of disease control compared to the absence of treatment when an appropriate level of damage caused by the disease appears on untreated leaf foliar discs (10 to 12 days after application).
[00216] [00216] The following mixing compositions (A: B) at the reported concentration (in ppm) gave at least 80% disease control in this test compared to untreated leaf control discs under the same conditions, which exhibit extensive disease development : Component A Component BA: conc. A: from B Rat (ppm) to
[00217] [00217] 4-week-old soy plants are sprayed in a spray chamber with the formulated test mixture compound or composition diluted in water. One day after application, the leaf discs are cut from treated plants and placed on agar, in 24-well plates. The leaf discs are inoculated by spraying with a spore suspension on the bottom surface of the leaf. After an incubation period of 24-36 hours in an air-conditioned chamber, in the dark, at 20 ºC and 75% of ur, the leaf discs are then kept at 20 ºC with 12 hours of light / day and at 75% of ur . The percentage of leaf disc area covered by disease is assessed when an appropriate level of disease appears in untreated control plants (12–14 days after application).
[00218] [00218] Leaf segments of wheat cv. Kanzler are placed on agar in multi-well plates (24-well format) and sprayed with the formulated test mixture compound or composition diluted in water. The leaf discs are inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf segments are incubated at 19 ºC and 75% of ur under a light regime of 12 hours of light / 12 hours of darkness in an air-conditioned chamber, and the activity of a compound or mixture composition is evaluated as a percentage control of disease, compared to the lack of treatment, when an appropriate level of damage caused by the disease appears in untreated leaf control segments (7 - 9 days after application).
[00219] [00219] Leaf segments of barley cv. Hasso are placed on agar in a multi-well plate (24-well format) and sprayed with the formulated test mixture compound or composition diluted in water. The leaf segments are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf segments are incubated at 20ºC and 65% of ur under a light regime of 12 hours of light / 12 hours of darkness in an air-conditioned chamber, and the activity of a compound or mixture composition is evaluated as disease control, compared to the absence of treatment, when an appropriate level of damage caused by the disease appears in untreated leaf control segments (5 - 7 days after application).
[00220] [00220] Fragments of mycelia from a newly cultivated liquid culture of the fungus are directly mixed in nutrient broth (potato broth and PDB dextrose). After placing a solution (DMSO) of the test compound or composition in a microtiter plate (96-well format), the nutrient broth containing the fungal material is added. The test plates are incubated at 24 ° C and the inhibition of growth is determined photometrically 3-4 days after application.
[00221] [00221] Leaf discoss of genetically modified soy (eg Understanding the MON87701 event; Intact soy RR2 PRO "!) Are placed in agar water in multi-well plates (24-well format) and sprayed with a compound selected from the compounds Q.001, Q.002, Q.003,
9,004, 90,005, 9,006, 9,007, 9,008, 9,009 and 0,010, as defined in Table Q above, or a fungicidal composition comprising a mixture of components (A) and (B) (as described above and claimed below) 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 75% of ur, the leaf discs are kept at 20 ºC with 12 h of light / day and 75% of ur. The activity of a compound or mixture composition is assessed as a percentage of disease control compared to the absence of treatment when an appropriate level of damage caused by the disease appears on untreated leaf disks (10 - 12 days after application).

权利要求:
Claims (17)
[1]
1. Fungicidal composition characterized by comprising a mixture of components (A) and (B), in which component (A) is a compound of formula (1) CH; R "cn, Rn
HO F F OCcH; 3 F (n), where Rº is ethyl, isopropyl or cyclopropyl (preferably ethyl or isopropyl); and Rº is -CH2C (= N-OC2Hs) CH3, n-butoxymethyl, cyclopropyl, cyclobutylmethoxymethyl, cyclopentoxymethyl, -CH2C (= CH2) CH3, n-butyl, phenyl, 2-methyl-phenyl or 3,5-difluorophenyl; or a salt, enantiomer, tautomer or N-oxide thereof; and component (B) is a compound selected from the group consisting of (B1) a strobilurin fungicide selected from the group consisting of azoxystrobin, picoxystrobin, enoxastrobin, piraoxystrobin, mandestrobin, fluphenoxystrobin, coumoxystrobin, orisastrobin, dimoxystrobin, phenytrobin, metominostrostrin, metominostrostrin, metominostrostrin, triclopyricarb, cresoxime-methyl, fluoxastrobin, pyribencarb, pyraclostrobin and trifloxystrobin; (B2) an azole fungicide selected from the group consisting of azaconazole, etaconazole, ipconazole, tebuconazole, bitertanol, fenbucoanzole, metconazole, tetraconazole, bromucoanzole, fluquinconazole, miclobutanil,
triadimefon, flusilazole, penconazole, triadimenol, triticonazole, simeconazole, imibenconazole, hexaconazole, flutriafol, diniconazole, ciproconazole, diphenoconazole, epoxiconazole, propiconazole, protioconazole, pyrifenox, trificon, pyrifenazole, trinicon, pyrifenazole, trificon [[3- (2-chlorophenyl) -2- (2,4-difluorophenyl) oxiran-2-yl] methyl] -4H- 1,2,4-triazol-3-thione and 2- [2-chloro-4 - (4-chlorophenoxy) phenyl] - 1- (1,2,4-triazol-1-yl) propan-2-ol;
(B3) a morpholine fungicide selected from aldimorph, dodemorph, fenpropimorph and tridemorph;
(B4) a carboxamide fungicide selected from bixafen, fluopyram, fluxpyroxade, isopyrazame, silkxane, furametpir, pyrflufen, pentiopyrade, benzovindiflupir, tifluzamide, isofetamide, boscalide, carboxine, oxycarboxine, mephonyl, pyridine, pyridine, pyridine, pyridine, pyridone, [(5-chloro-2-isopropyl-phenyl) methyl] -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-pyrazol-4-carboxamide, 3- (di-fluoromethyl) -N- (7 -fluoro-1,1,3-trimethyl-indan-4-1yl) -l-methyl-pyrazol-4-carboxamide, 3- (difluoromethyl) -1-methyl-N- (1,1,3-trimethylindan-4 -yl) pyrazol-4-carboxamide and (R) -3- (difluoromethyl) -1-methyl-N- (1,1,3-trimethylindan-4-
il) pyrazol-4-carboxamide;
(B5) an anilinopyrimidine fungicide selected from cyprodinil, mepanipyrim and pyrimethanil;
(B6) a phenylpyrrole fungicide selected from fludioxonil and fenpiclonil;
(B7) a phenylamide fungicide selected from benalaxyl, benalaxyl-M, furalaxyl, mefenoxam (metalaxyl-M) and metalaxyl, ofurace and oxadixyl;
(B8) a fungicide selected from the group consisting of ametoctradine, amisulbrome, anilazine, aureofungin, benomile, bentiavalicarb, bentiazole, betoxazine, BLAD, blasticidin-S, mixture Bordeaux, bupyrimate, calcium polysulfide, captafol, carbendamide, carbamide, carbamide, carbamide, carbamide, carbamide, carbamide , cinomethionate, chitosan, clobentiazone, chlorphenazole, chloroneb, chlorothalonil, clozolinate, climbazol, copper acetate, copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper oxyquinolate, copper silicate, sulfate copper, copper talate, cuprous oxide, cyzofamide, cyclamfuramide, cyflufenamide, cymoxanil, dazomete, diclofluanide, dichlorprope, diclocimet, diclomezine, dichlorane, dietofencarb, diflumetorime, dimethacrone, dinetone, dinetone, dimetone, dimetone, dipimethitrone, ditalymhos, dithianone, dodicin, dodine, doguadine, edifenfós, eteme, etaboxame, etirimol, ethoxyquin, etridiazole, famoxad one, fenamidone, fenarimol, fen-hexamide, fenoxanil, fenpropidina, fenpyrazamina, fentina acetate, fentina hydroxide, ferbame, ferimzona, fluaziname, flumorfe, fluopicolida, fluoroimida, flusulfamide, flutianila, folpete, fiberethyl-acid, fiberethyl-aldehyde; , guazatin, himexazole, iminoctadine, iodocarb, iprobenfós, iprodione, iprovalicarb, isoprothiolane, casugamycin, mancozebe, mandipropamide, manebe, metame, meptildinocape, metamame, metrafenone, nabame, oxathiaproline,
paclobutrazol, pencicurone, phenamacryl, phosdiphen, phthalide, picarbutrazox, polyoxin D, probenazole, procymidone, pro- hexadione, propamocarb, propineb, proquinazide, pyrazophos, pirifenox, pyrimorphine, pyrophylline, pyroxyphenone, pyroxyphenone, pyroxoxamine, , tebufloquina, keyboardophthalam, tecnazene, thiabendazole, tidiazurone, thiciofen, thiophanate-methyl, thiram, thioximide, tolclofós-methyl, tolprocarb, tolylfluanide, triazoxide, tribufós, triciclazol, triforina, validifazine, valaminine, valaminine, valamininaine , [2- [3- [2- [1- [2- [3,5-bis (difluoromethyl) pyrazol-11-yl] acetyl] -4-piperidyl] thiazol-4-11] -4,5 methanesulfonate -dihydroisoxazol-5-yl] -3-chloro-phenyl], N- [6- [[(2) - [(1-methylthetrazol-5-yl) -phenylmethylene] amino] oxymethyl] -2- pyridyl] but-3-inyl carbamate, N '- [4- (4,5-dichlorothiazole-2-11) oxy-2,5-dimethyl-phenyl] -N-ethyl-N-methyl-formamidine, 4- (2-bromo-4-fluoro-phenyl) -N- (2-chloro-6-fluoro-phenyl) -2,5-dimethyl-p irazol-3-amine, 2- [2-fluoro-6 - [(8-fluoro-2-methyl-3-quinolyl) oxy] phenyl] propan-2-ol, 4,4, 5-trifluoro-3,3 - dimethyl-1- (3-quinolyl) isoquinoline, 3-chloro-6-methyl-5-phenyl-4- (2,4,6-trifluorophenyl) pyridazine, 3-chloro-4- (2,6-difluorophenyl) -6-methyl-5-phenyl-pyridazine, 2-7 (di fluoromethyl) -N- (1,1,3-trimethylindan-4-yl) pyridine-3-carboxamide, 2- (difluoromethyl) -N- (3 -ethyl-1,1-dimethyl-indan-4-yl) pyridine-3-carboxamide, 2- (difluoromethyl) -N- (1,1-dimethyl-3-propyl-indan-4-yl) pyridine-3- carboxamide, 2-7 (di-fluoromethyl) -N- (3-isobutyl-1,1-dimethyl-indan-4-yl) pyridine-3-carboxamide, 2- (difluoromethyl) -N - [(3R) -1, 1,3-trimethylindan-4-yl] pyridine-3-carboxamide, 27
(difluoromethyl) -N - [(3R) -3-ethyl-1,1-dimethyl-indan-4-yl] pyridine-3-carboxamide, 2- (difluoromethyl) -N - [(3R) -1,1- dimethyl-3-propyl-indan-4-yl] pyridine-3-carboxamide, a compound of the formula
F
F
F
TN H
NX, a compound of formula to Vas
F N
AND /
NX, and a compound of formula: Gives
L A o o O ó OZ | nego B & N H o (B9) a plant bioregulator selected from the group consisting of acibenzolar-S-methyl, clormequate chloride, etefone, isothianyl, mepiquate chloride, thiadinyl and trinexapacethyl; (B10) an insecticide selected from the group consisting of abamectin, acequinocyl, acetamipride, acrinatrine, aphidopyropene, alanicarb, aletrine, alpha-cypermethrin,
alfamethrin, amidoflumete, azadiractin, azocyclotin, bacillus firmus, bacillus thuringiensis, bensultape, benzoximate, betaciflutrin, bifenazate, binapacrilla, bioalethrin, bioresmethrin, bifentrine, broflanilide, broflutrin, carbofluorine, etherol, carboform, chloroform chlorfenapyr, chromafenozide, cloetocarb, clothianidin, cyantraniliprol, cyclaniliprol, cycloprotrin, cycloxapride, cyienopyraphene, cyphlumetofen, cyfluthrin, cyhalothrin, diphtheria, dyrometin, dyrometrin, dyrometrin, dyromethazine, diamethylamine dinocape, dinotefuran, d-limonene, emamectin, empentrine, sphenolvalerate, ethione, etiprol, etofenprox, ethoxazole, fanfur, phenazaquin, fenflutrin, phenobucarb, phenoxycarb, fenpropatrine, fenpyroximate, fluvamimide, flimamimide, flimimimide, flimimide, fluprimine flucitrinate, fluensulfone, flufenerime, flufenprox, f lufiprol, fluhexafone, flumethrin, flupyradifurone, fluvalinate, fostiazate, gamma-cyhalothrin, gossiplur, guadipir, halofenozide, halofenprox, harpine, hexitiazox, hydramethylnone, imiciafosine, imidacidamide, isidacid, imidaclidate lepimectin, lufenurone, metaflumizone, metallohyde, methoxy, methoxyfenozide, metoflutrin, milbemectin, niclosamide, nitenpirame, oxamyl, parathione-ethyl, Pasteuria nishizawae, p-cimene, permethrin, etherine, phosphocarbon, pyropyrimide, pyronoxide, piperine , pralethrin, profenofós, profenofós, propargita, propetanfós,
protrifenbute, piflubumide, pimetrozine, piraclofós, pirafluprol, piretrum, pyridaben, pyridalil, pyrifluquinazone, pyrimidifen, pyriprol, pyriproxifene, selamectin, silafluofen, spinach, tepid, spinoxide, tyrophosphorphite, spirodyroform, spirodichloride terpenoids, tetradifone, tetramethrin, tetranactin, tetraniliprol, teta-cypermethrin, thiaclopride, thiamethoxam, tiodicarb, tioxazafene, tolfenpirade, transflutrin, trichlorphone, triflumezopyrim, zeta-cypermethrin and a-terpine;
(B11) glyphosate;
(B12) a compound selected from the group consisting of:
Azoxystrobin
NODE No. CAS: Je 131860-33-8 o o | Ap Sse>
No Trifloxistrobi R FE in
F No. CAS: O 141517-21-7 o
É / Picoxistrobina Nº. CAS: N7 / 117428-22-5 F = | o R o ON o 1- [2 - [[1- (4-7 chlorophenyl) pyrazol-3-yl] Joximethyl] - 3-methyl-phenyl1] -4-methyl-5-O. tetrazole-5- ona 7X cl N (for = N preparation, Ç see WO no 2013/162072) Coumoxistrobin NX to Nº. CAS: DSR o XX 850881-70-8 o o o
Ciproconazol to No. CAS: -06- N 94361-06-5 O HO = =, Difenoconazole No. CAS: F. : "NNE 119446-68-3 N at 9 AX. Tebuconazole CAS No.: O 107534-96-3 SS Protioconazole! CAS No.: W 178928-70-6 —N cl N y dr
S H Hexaconazole No. CAS: 79983-71-4 od a NG Cc
Mefentriflucon azol nº. CAS: 1417782-03-6 (2RS) -2- [4- (4-chlorophenoxy) - a, a, A-trifluoro-o-tolyl] -1- (1H- 1,2,4-triazole- F 1 -il) propan-2- Ff FH ol [e (for preparation, N. see WO o Né 7 2013/007767) x Fenpropidine Nº. CAS: 67306- O 00-7 Fenpropimorfe E Enantiomer qN A Nº. CAS: 67564- 91-4 | Bixafen c cl Nº. CAS: h O
ITA F 581809-46-3 & —N H = N. TO. Fluxapiroxade
AND NO. CAS: r TN + 907204-31-3 LS O
F F
F
Isopyrazame and Enantiomer No. CAS: CA 881685-58-1 o NH
F e: tl
NX Sedaxano Nº. CAS: FR
H 874967-67-6 [y / o
Benzovindiflup and enantiomer ir ca 1 Nº. CAS: O, H 1072957-71-1 x F; N — N
NX Pidiflumetofen / o | | N LO »Nº. CAS: 1228284-64-7 o F cl Cl F 3- (difluoromethyl) -1-methyl-N- [(3R) -1,1,3-trimethylindan-4-yl] pyrazole-4-carboxamide DR
F N Í (for 'preparation, it is À consult WO 2011/162397)
Isofluciprame No. CAS: 1255734-28-1 N- [(5-chloro-2-isopropyl-phenyl) methyl] - N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-pyrazole-4-carboxamide [à ( for F VT N preparation, NR NV see WO NF 2010/130767) | à Structure compound: (for preparation, mm consult WO JJ o 2014/095675) À F Sy
F Compound of F. F structure: (for 'RR preparation, | H see WO PÁ SS 2014/095675) À
Y13149 N- [2- [2-chloro- 4- (trifluoromethyl) phenoxy] phenyl 1-3- (difluoromethyl (ng) -1-methyl-, FN | pyrazolo-4- / À H carboxamide Ne o (para | F preparation, F see WO F 2015058444) Fluindapyr No. Cas: 1383809-87-7 3- (difluoromethyl) -N- (7-fluoro-1,1,3-trimethyl-indan-4-yl) - 1-methyl - pyrazolo-4- F carboxamide [n (for F preparation, TS see WO 2012/084812) | Fenpicoxamide nº. Cas: 517875-34-2 o.
Á N (for preparation, and N, 'see WO | YA 2003/035617) NX F
Chlorothalonil Cl N
PAN
RR Nº. CAS: 1897- 45-6 cl Cc Cc Mancozebe O) Ss O) j Nº. CAS: 8018 N IS N E. : - M n LI> LI ”01-7 Ss S S Ss Spiroxamine Nº. CAS: 118134-30-8 N-ethyl-N-propyl-8-tert-butyl-1,4-CHz3 fo) NO CH dioxaspiro [4.5 HC 3 3] dec-2- o (cHs ilmethylamine CHz3 (B13) um insecticide selected from the group consisting of 3- (4-chloro-2,6-dimethyl-phenyl) -8-methoxy-1-methyl-2-oxo-1,8-diazaspiro carbonate [4.5] dec-3-en- 4-yl] ethyl (spiropidion), chlorantraniliprol, cyantraniliprol, abamectin, emamectin benzoate, thiamethoxam, acetamipride and diafentiurone; (B14) a herbicide selected from the group consisting of Glyphosate, Dicamba, 2,4-dichlorophenoxy acid (2,4-dichlorophenoxy acid) D and Glufosinate; (B15) a biostimulating protein hydrolyzate commercially available as "Isabion" 7 “; (Bl6) a biofungicide comprising strains of Bacillus subtilis, such as Taegrod (a biofungicide comprising the FZB24 strain of Bacillus subtilis var. Amyloliquefaciens), Serenade (based on the QOST713 strain) or Subtilex (based on the MBI600 strain);
(B17) a bioinsecticidal product comprising one or more lolino alkaloids, such as N-formyl-lolina and especially the lolino alkaloids compositions obtained by the processes described in WO2016091987;
(B18) a compound selected from X.01, X.02, X.03, X.04, X.05, X.06, X.07, X.08, X.09, X.10, X.11 , X.12, X.13, X.14, X.15, X.16, X.17, X.18, X.19, X.20, X.21, X.22 and X.23 in the Table X below:
Table X Xx.01l Q on Ne N-methoxy-N - [[4- [5- “o 4 OR. (trifluoromethyl) -1,2,4- F oxadiazol-3-yl] phenyl] methyl] cyclopropa nocarboxamide x.02 À N-methoxy-N - [[4- [5-% 2 POA F (trifluoromethyl) -1, 2,4- Í EA! ; In oxadiazol-3-yl] phenyl] methyl] pent-4-inamide x.03 ff N -— methoxy-2-methyl-N - [[4- SO F r [5- (trifluoromethyl) - Ss 1,2, 4-0oxadiazol-3-yl] phenyl] methyl] prop-2-enamide
Structure of the compound name IUPAC x.04 À N, 2-dimethoxy-N - [[4- [5- o SO, F (trifluoromethyl) -1,2,4-
F í + No oxadiazol-3-yl] phenyl] methyl] propanamid at x.05 EX N-cyclopropyl-3,3,3- F FO F trifluoro-N - [[4- [5-
F í + No (trifluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] propanamid ao x.06 A 2,2-difluoro-N- (2- F 2a F methoxyethyl) -N- [ [4- [5- AT | dogs; o NO r (trifluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] cyclopropa nocarboxamide x.07 FP N-ethyl-2-methyl-N - [[4- [5- ey (trifluoromethyl) -1,2,4- o Proxadiazol-3-yl] phenyl] methyl] propanamid NE oa Xx.08 We. N - [[3-fluoro-4- [5- if F (trifluoromethyl) -1,2,4- I TA NO FF oxadiazol-3-yl] phenyl] methyl] -N-methoxy-propanamide
Compound structure IUPAC name x.09 x 2-methoxy-N- (2,2,2- DD ne trifluoroethyl) -N - [[4- [5- / ES Ao (trifluoromethyl) -1,2,4-
F oxadiazol-3-11] phenyl] methyl] acetamide x.10 À Ff; N - [[2,3-difluoro-4- [5- DX. F (trifluoromethyl) -1,2,4- TA NO FF oxadiazol-3-yl] phenyl] methyl] -N-methoxy-cyclopropanecarboxamide o Xx.11 RA 2- (di fluoromethoxy) -N- | F il-N- - [5- F O is | methyl-N - [[4- [5 No EF (trifluoromethyl) -1,2,4-oxadiazol-3- 11] phenyl] methyl] acetamide X.12 FAN F N-ethoxy-2-methoxy-N - [[ 4- and [5- (trifluoromethyl) - o, Pr 1,2,4-0xadiazol-3-yl] phenyl] methyl] propanamid AP o “7 º o 'Xx.13 N-isopropyl-N - [[4- [5- kh (trifluoromethyl) -1,2,4- o-oxadiazol-3-yl] phenyl] methyl] tetra- READ hydrofuran-2-carboxamide
F
F
Structure of the compound IUPAC name x.14 1-methoxy-3-methyl-1 - [[4- HN N; I DO, [5- (trifluoromethyl) - Ss N ne 1,2,4-0xadiazol-3-Fx Fyl] phenyl] methyl] urea X.15 O 3-cyclopropyl-1-methoxy-1-
HN Pro [[4- [5- (trifluoromethyl) - 1,2,4-0xadiazol-3-yl] phenyl] methyl] urea o
LF
F
FF x.16 Is 3-ethoxy-l-methoxy-l - [[4- o: HNº [5- (tri fluoromethyl) - ok Í o 1,2,4-0oxadiazol-3- LS 11] phenyl] methyl] urea o
READ
F
FF x.17 DÉ 3-allyl-1-methoxy-1l - [[4- [5- H (trifluoromethyl) -1,2,4-
Oxadiazol-3-SS il] phenyl] methyl] urea o
FF Nx, x.18 and AR 1-cyclopropyl-3-methoxy-3- = F AS F methyl-1 - [[4- [5- Fu (trifluoromethyl) -1,2,4-
Structure of the compound IUPAC name oxadiazol-3- 11] phenyl] methyl] urea X.19 s 3-isopropyl-l-methoxy-l1-
HN Ah EO. [[4- [5- (trifluoromethyl) - x Z2N. 1,2,4-0xadiazol-3-PDyl] phenyl] methyl] urea X.20 o k l-methoxy-3-prop-2-ynyl-1- N No., H | OA, [[4- [5- (trifluoromethyl) - = F
N / t F 1,2,4-0oxadiazol-3-yl] phenyl] methyl] urea x.21 5 1 - [[3-fluoro-4- [5- HN ON; ; I look. (trifluoromethyl) -1,2,4-
SN ne oxadiazol-3-FX FX] phenyl] methyl] -l-methoxy-3-methyl-urea x.22 y 3- (cyclopropylmethyl) -1- HN methyl-1 - [[4- [5- so ( trifluoromethyl) -1,2,4- OS oxadiazole-3-
F FIA 7 yl] phenyl] methyl] urea F or N x.23 Y 1-ethyl-3- (2,2,2- Ho trifluoroethyl) -1 - [[4- [5- Ao (trifluoromethyl) -1, 2,4- OS oxadiazole-3-F; 1] phenyl] methyl] urea F 7 1 +
PA and (B19) a compound selected from Y.01, Y.02, Y.03, Y.04, Y.05, Y.06, Y.07, Y.08, Y.09, Y.10, Y .11, Y.12, Y.13, Y.14, Y.15, Y.16, Y.17, Y.18 and Y.19 in Table Y below: Table Y v.0o1 R 1 - [[4 - [5- CA, (trifluoromethyl) -1,2,4- SS oxadiazol-3- "” yl] phenyl] methyl] pyrrolidin —2-one v.02 P 1 - [[4- [5- OQ. (trifluoromethyl) -1,2,4- = oxadiazol-3-Ds] phenyl] methyl] piperidin-2-0one v.o3 4 4 - [[4- [5- OQ. (trifluoromethyl) -1,2, 4- = oxadiazol-3- E 11] phenyl] methyl] morpholin-3-one Y.04 AIRE 4, 4-dimethyl-2 - [[4- [5- Q = E (trifluoromethyl) -1,2, 4- oxadiazol-3-yl] phenyl] methyl] isoxazolid in-3-one Y.05 AJA) 2 - [[4- [5- o “x (trifluoromethyl) -1,2,4- oxadiazole-3-
ops tt in-3-one v.06 AV 5,5-dimethyl-2 - [[4- [5- PN o “x (trifluoromethyl) -1,2,4- oxadiazol-3-yl] phenyl] methyl] isoxazolid in-3-one v.07 v 3,3-dimethyl-1 - [[4- [5- OA, (trifluoromethyl) -1,2,4- / oxadiazol-3-Sdyl] phenyl] methyl] piperidin - 2-0 in v.o8 Q '1 - [[2-fluoro-4- [5- SO (trifluoromethyl) -1,2,4- = oxadiazol-3-DD yl] phenyl] methyl] pyrrolidin —2-one v.09 o '1 - [[2-fluoro-4- [5- Sac (trifluoromethyl) -1,2,4- = oxadiazol-3- DD yl] phenyl] methyl] piperidin- 2-0na Y.10 uv 2 - [[4- [5- CA, (trifluoromethyl) -1,2,4- yl oxadiazol-3-] phenyl] methyl] oxazinan-3-one
Y.11 and 1 - [[3-fluoro-4- [5- eae F (trifluoromethyl) -1,2,4- KSA oxadiazol-3-yl] phenyl] methyl] piperidin-2-0one Y.12 NS Er 3 - [[4- [5- SS (trifluoromethyl) -1,2,4-oxadiazol-3- no) 11] phenyl] methyl] oxazolidin —2-one v.13 À 1-methyl-3 - [[4 - [5- IA: (trifluoromethyl) -1,2,4- o oxadiazol-3-F F il] phenyl] methyl] imidazolid in-2-one Y.14 o 1 - [[3-fluoro-4- [ 5- UN, F (trifluoromethyl) -1,2,4- ESA, oxadiazol-3-yl] phenyl] methyl] -3,3-dimethyl-piperidin-2-one Y.15 Q 1 - [[3-fluoro -4- [5- IA F (trifluoromethyl) -1,2,4- F EIA, oxadiazol-3-yl] phenyl] methyl] pyrrolidin —2-one Y.16 XÁ F 2 - [[3-fluoro-4 - [5- the “O.
F (trifluoromethyl) -1,2,4- ET! oxadiazol-3-yl] phenyl] methyl] -4,4-
= one Y.17 g 2 - [[2,3-difluoro-4- [5- SAD t, (trifluoromethyl) -1,2,4- No oxadiazol-3-yl] phenyl] methyl] isoxazolid in-3- Y.18 Ç 2 - [[3-fluoro-4- [5- SA, (trifluoromethyl) -1,2,4- f NO E oxadiazol-3-yl] phenyl] methyl] isoxazolid in-3-one v .19 v 1 - [[4- [5- SA (trifluoromethyl) -1,2,4- oxadiazol-3-yl] phenyl] methyl] azepan-2-one or a salt, enantiomer, tautomer or N -oxide; and wherein the weight ratio of component (A) to component (B) is 40: 1 to 1:40.
[2]
Fungicidal composition according to claim 1, characterized in that component (A) is a compound or a salt, enantiomer, tautomer or N-oxide, selected from N '- [4 - [(3E) -3- ethoxy-imino-1-hydroxy-1- (trifluoromethyl) butyl] -5-methoxy-2-methyl-phenyl] -N-ethyl-N-methyl-formamidine (compound Q.001);
N '- [4- [1- (butoxymethyl) -2,2,2-trifluoro-1-hydroxy-ethyl] - 5-methoxy-2-methyl-phenyl] -N-ethyl-N-methyl-formamidine (compound 90,002); N '- [4- (1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl) -5-methoxy-2-methyl-phenyl] -N-isopropyl-N-methyl-formamidine (compound 0.003) ; N '- [4- [1- (cyclobutylmethoxymethyl) -2,2,2-trifluoro-1-hydroxy-ethyl] -5-methoxy-2-methyl-phenyl] -N-ethyl-N-methyl-formamidine (compound Q.004); N '- [4- [1- (cyclopentoxymethyl) -2,2,2-trifluoro-1-hydroxy-ethyl] -5-methoxy-2-methyl-phenyl] -N-ethyl-N-methyl-formamidine (compound Q.005); N '- [4- [1-hydroxy-3-methyl-1- (trifluoromethyl) but-3-enyl] - 5-methoxy-2-methyl-phenyl] -N-isopropyl-N-methyl-formamidine (compound 0.006 ); N '- [4- [1-hydroxy-l1- (trifluoromethyl) pentyl] -5-methoxy-2-methyl-phenyl] -N-isopropyl-N-methyl-formamidine (compound
92,007); N-isopropyl-N '- [5-methoxy-2-methyl-4- (2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl) phenyl] -N-methyl-formamidine (compound 0.008); N-ethyl-N '- [5-methoxy-2-methyl-4- [2,2,2-trifluoro-1-hydroxy-1- (o-tolyl) ethyl] phenyl] -N-methyl-formamidine (compound 0.009); and N '- [4- [1- (3,5-difluorophenyl) -2,2,2-trifluoro-1-hydroxy-ethyl] -5-methoxy-2-methyl-phenyl] -N-ethyl-N- methylformamidine (compound 0.010).
[3]
Fungicidal composition according to any one of claims 1 and 2, characterized in that component (B) is a compound selected from the group consisting of:
(B12) a compound selected from the group consisting of: Azoxystrobin (No.
CAS: 131860-33-8), Trifloxystrobin (No.
CAS: 141517-21-7), Picoxystrobin (Nº.
CAS: 117428- 22-5), 1- [2 - [[1- (4-chlorophenyl) pyrazol-3-yl] oxymethyl] -3-methyl-phenyl] -4-methyl-tetrazol-5-one (from WO 2013/162072), Coumoxystrobin (No.
CAS: 850881-70-8), Ciproconazole (Nº.
CAS: 94361-06-5), Difenoconazole (Nº.
CAS: 119446-68-3), Tebuconazole (No.
CAS: 107534-96-3), Protioconazole (Nº.
CAS: 178928-70-6), Hexaconazole (No.
CAS: 79983-71-4), Mefentrifluconazole (CAS No.: 1417782-3-6; (2RS) -2- [4- (4-chlorophenoxy) -a, a, a-trifluoro-o-tolyl] -1- (1H-1,2,4-triazol-11-yl) propan-2-ol; from WO 2013/007767), Fenpropidine (No.
CAS: 67306-00-7), Fenpropimorfe (Nº.
CAS: 67564-91-4), Bixafeno (Nº.
CAS: 581809-46-3), Fluxapiroxade (Nº.
CAS: 907204-31-3)
Isopyrazam (Nº.
CAS: 881685-58-1), Sedaxane (No.
CAS: 874967-67-6), Benzovindiflupir (No.
CAS: 1072957-71-1), Pidiflumetofen (Nº.
CAS: 1228284-64-7), 3- (di fluoromethyl) -l-methyl-N - [(3R) -l1,1,3-trimethylindan-4-
il] pyrazolo-4-carboxamide (from WO 2011/162397)
Isofluciprame (No.
CAS: 1255734-28-1; N - [(5-chloro-2-isopropyl-phenyl) methyl] -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-pyrazolo-4-carboxamide; from WO
HN d Sw
2010/130767), a structure compound (for preparation, see WO 2014/095675), a compound of
F F | H
To the structure (for preparation, see WO 2014/095675), a compound of structure: F o NO OO i (Y13149; N- [2- [2-chloro-4- (tri fluoromethyl) phenoxy] phenyl] -3- (difluoromethyl) -1-methyl-pyrazolo-4-carboxamide; from WO 2015/058444) Fluindapyr (Cas no .: 1383809-87-7; 3- (difluoromethyl) -N- (7-fluoro-1,1,3 -trimethyl-indan-4-11) -l-methyl-pyrazolo-4-carboxamide; from WO 2012/084812), Fenpicoxamide (No. Cas: 517875-34-2; from WO 2003/035617), Chlorothalonil (No. CAS: 1897-45-6), Mancozebe (CAS No.: 8018-01-7), Spiroxamine (CAS No.: 118134-30-8; N-ethyl-N-propyl-8-tert-butyl-1, 4-dioxaspiro [4.5] dec-2-ylmethylamine); (B13) an insecticide selected from the group consisting of 3- (4-chloro-2,6-dimethyl-phenyl) -8S-methoxy-1-methyl-2-oxo-1,8-diazaspiro [4.5] dec- 3-en-4-yl] ethyl (spiropidion), chlorantraniliprol, cyantraniliprol, abamectin, emamectin benzoate, thiamethoxam, acetamipride and diafentiurone; (B14) a herbicide selected from the group consisting of Glyphosate, Dicamba, 2,4-dichlorophenoxyacetic acid (2,4-D) and Glufosinate;
(B15) a biostimulating protein hydrolyzate commercially available as "Isabion" "*"; (B16) a biofungicide comprising strains of Bacillus subtilis, such as TaegroO (a biofungicide comprising the FZB24 strain of Bacillus subtilis var. Amyloliquefaciens), Serenade6O (based on the QOST713 strain) or Subtilexo (based on the MBI600 strain); (B17) a bioinsecticidal product comprising one or more lolino alkaloids, such as N-formyl-lolina and especially the lolino alkaloids compositions obtained by the processes described in WO2016091987; (B18) a compound selected from N-methoxy-N - [[4- [5- (trifluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] cyclopropanecarboxamide (compound X.01), N- methoxy-N - [[4- [5- (trifluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] pent-4-inamide (compound Xx.02), N-methoxy-2-methyl -N - [[4- [5- (trifluoromethyl) -1,2,4- oxadiazol-3-11] phenyl] methyl] prop-2-enamide (compound Xx.03), N, 2-dimethoxy-N- [[4- [5- (trifluoromethyl) -1,2,4-oxadiazole-3-1yl1] phenyl] methyl] propanamide (compound X.04), N-cyclopropyl-3,3,3-trifluoro-N- [ [4- [5- (trifluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] propanamide (compound X.05), 2.27 difluoro-N- (2-methoxyethyl) -N- [ [4- [5- (trifluoromethyl) - 1,2,4-0oxadiazol-3-yl] phenyl] methyl] cyclopropanecarboxamide (compound X.06), N-ethyl-2-methyl-N - [[4- [5 - (trifluoromethyl) -1,2,4- oxadiazole-3-1yl] phenyl] methyl] propanamide (compound X.07), N - [[3-fluoro-4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl] phenyl] methyl] -N-methoxy-propanamide (compound X.08),
2-methoxy-N- (2,2,2-trifluoroethyl) -N - [[4- [5- (trifluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] acetamide (compound X. 09), N - [[2,3-difluoro-4- [5- (trifluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] -N-methoxy-cyclopropanecarboxamide (compound X.10) , 2- (difluoromethoxy) -N-methyl-N - [[4- [5- (trifluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] acetamide (compound X.11), N- ethoxy-2-methoxy-N - [[4- [5- (trifluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] propanamide (compound X.12), N-isopropyl-N- [ [4- [5- (trifluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] tetrahydrofuran-2-carboxamide (compound X.13), 1-methoxy-3-methyl-l- [[4- [5- (trifluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] urea (compound X.14), 3-cyclopropyl-1-methoxy-l - [[4- [ 5- (trifluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] urea (compound X.15), 3-ethoxy-1-methoxy-1 - [[4- [5- (trifluoromethyl)) -1,2,4-oxadiazol-3-yl] phenyl] methyl] urea (compound Xx.16), 3-allyl-1-methoxy-1 - [[4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl] phenyl] methyl] urea (compound X.17), l-cyclopropyl-3-methoxy-3-methyl-l1 - [[4- [5- (tri fluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] urea (compound X.18), 3-isopropyl-l1- methoxy-l - [[4- [5- (trifluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] urea (compound X.19), 1-methoxy-3-prop- 2-ynyl-11 - [[4- [5- (trifluoromethyl) -1,2,4-0xadiazol-3-yl] phenyl] Jmetyl] urea (compound X.20), 1 - [[3-fluoro-4- [5- (tri-fluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] - 1-methoxy-3-methyl-urea (compound X.21), 3- (cyclopropylmethyl) -l-methyl-l - [[4- [5- (trifluoromethyl) -
1,2,4-0xadiazol-3-yl] phenyl] methyl] urea (compound X.22), 1-ethyl-3- (2,2,2-trifluoroethyl) -1 - [[4- [5- ( trifluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] urea (compound X.23) in Table X above; and (B19) a compound selected from 1 - [[4- [5- (trifluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] pyrrolidin-2-one (compound Y.01), 1 - [[4- [5- (tri fluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] piperidin-2-one (compound Y.02), 4 - [[4- [5- (tri fluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] morpholin-3-one (compound Y.03), 4.4 dimethyl-2 - [[4- [5- (trifluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] isoxazolidin-3-one (compound Y.04), 2- [[4- [5- (tri fluoromethyl) -1,2,4-oxadiazole -3- yl] phenyl] methyl] isoxazolidin-3-one (compound Y.05), 5,5-dimethyl-2 - [[4- [5- (trifluoromethyl) -1,2,4-oxadiazole-3- yl] phenyl] methyl] isoxazolidin-3-one (compound Y.06), 3,3-dimethyl-1 - [[4- [5- (trifluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl ] methyl] piperidin-2-one (compound Y.07), 1 - [[2-fluoro-4- [5- (trifluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] Jmetyl] pyrrolidin- 2-one (compound Y.08), 1 - [[2-fluoro-4- [5- (tri-fluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] piperidin-2-one ( compound Y.09), 2 - [[4- [5- (tri fluoromethyl) -1,2,4- oxadiazol-3-yl] phenyl] methyl] oxazinan-3-one (compound Y.10), 1 - [[3-fluoro-4- [5- (trifluoromethyl) -1,2,4-0oxadiazol-3-yl ] phenyl] methyl] piperidin-2-one (compound Y.11), 3 - [[4- [5- (tri fluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] oxazolidin-2 -one (compound - “Y.12), 1- methyl-3 - [[4- [5- (trifluoromethyl) -1,2,4-oxadiazole-3-
yl] phenyl] methyl] imidazolidin-2-one (compound Y.13), 1- [[3-fluoro-4- [5- (trifluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl ] -3,3-dimethyl-piperidin-2-one (compound Y.14), 1 - [[3-fluoro-4- [5- (trifluoromethyl) -1,2,4-oxadiazole-3-11] phenyl ] methyl] pyrrolidin-2-one (compound Y.15), 2 - [[3-fluoro-4- [5- (trifluoromethyl) -1,2,4- oxadiazol-3-11] phenyl] methyl]) - 4,4-dimethyl-isoxazolidin-3-one (compound Y.16), 2 - [[2,3-difluoro-4- [5- (tri fluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] isoxazolidin-3-one (compound Y.17), 2- [[3-fluoro-4- [5- (trifluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] isoxazolidin -3-one (compound Y.18), 1- [[4- [5- (tri-fluoromethyl) -1,2,4-oxadiazol-3-yl] phenyl] methyl] azepan-2-one (compound I. 19) in Table I above; or a salt, enantiomer, tautomer or N-oxide thereof.
[4]
Fungicidal composition according to any one of claims 1, 2 and 3, characterized in that component (A) is N '- [4 - [(3E) -3-ethoxy-imino-1-hydroxy-1- (tri fluoromethyl) butyl] -5-methoxy-2-methyl-phenyl] -N-ethyl-N-methyl-formamidine (compound Q.001); or a salt, enantiomer, tautomer or N-oxide thereof.
[5]
Fungicidal composition according to any of claims 1, 2 and 3, characterized in that component (A) is N '- [4- [1- (butoxymethyl) -2,2,2-trifluoro-1-hydroxy- ethyl] -5-methoxy-2-methyl-phenyl] -N-ethyl-N-methyl-formamidine (compound 0.002); or a salt, enantiomer, tautomer or N-oxide thereof.
[6]
Fungicidal composition according to any of claims 1, 2 and 3, characterized in that the component
(A) be N '- [4- (1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl) -5-methoxy-2-methyl-phenyl] -N-isopropyl-N-methyl-formamidine (compound 0.003); or a salt, enantiomer, tautomer or N-oxide thereof.
[7]
Fungicidal composition according to any of claims 1, 2 and 3, characterized in that component (A) is N '- [4- [1- (cyclobutylmethoxymethyl) -2,2,2-trifluoro-l-hydroxy- ethyl] -5-methoxy-2-methyl-phenyl] -N-ethyl-N-methyl-formamidine (compound Q.004); or a salt, enantiomer, tautomer or N-oxide thereof.
[8]
Fungicidal composition according to any of claims 1, 2 and 3, characterized in that component (A) is N '- [4- [1- (cyclopentoxymethyl) -2,2,2-trifluoro-1-hydroxy- ethyl] -5-methoxy-2-methyl-phenyl] -N-ethyl-N-methyl-formamidine (compound 0.005); or a salt, enantiomer, tautomer or N-oxide thereof.
[9]
Fungicidal composition according to any of claims 1, 2 and 3, characterized in that component (A) is N '- [4- [1-hydroxy-3-methyl-l- (trifluoromethyl) but-3-enyl ] -5-methoxy-2-methyl-phenyl] -N-isopropyl-N-methyl-formamidine (compound 0.006); or a salt, enantiomer, tautomer or N-oxide thereof.
[10]
Fungicidal composition according to any of claims 1, 2 and 3, characterized in that component (A) is N '- [4- [11-hydroxy-1- (trifluoromethyl) pentyl] -5-methoxy-2- methyl-phenyl] -N-isopropyl-N-methyl-formamidine (compound 0.007); or a salt, enantiomer, tautomer or N-oxide thereof.
[11]
11. Fungicidal composition according to any of claims 1, 2 and 3, characterized in that the component
(A) be N-isopropyl-N '- [5-methoxy-2-methyl-4- (2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl) phenyl] -N-methyl-formamidine ( compound 0.008); or a salt, enantiomer, tautomer or N-oxide thereof.
[12]
Fungicidal composition according to any of claims 1, 2 and 3, characterized in that component (A) is N-ethyl-N '- [5-methoxy-2-methyl-4- [2,2,2- trifluoro-1-hydroxy-1- (o-tolyl) ethyl] phenyl] -N-methyl-formamidine (compound 0.009); or a salt, enantiomer, tautomer or N-oxide thereof.
[13]
13. Fungicidal composition according to any of claims 1, 2 and 3, characterized in that component (A) is N '- [4- [1- (3,5-difluorophenyl) -2,2,2-trifluoro- 1-hydroxy-ethyl] -5-methoxy-2-methyl-phenyl] -N-ethyl-N-methyl-formamidine (compound 0.010); or a salt, enantiomer, tautomer or N-oxide thereof.
[14]
Fungicidal composition according to any one of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13, characterized in that the composition comprises one or more additional pesticides selected from the group consisting of: a fungicide, selected from etridiazole, fluazinam, benalaxyl, benalaxyl-M (chiralaxyl), furalaxyl, metalaxyl, metalaxyl-M (mefenoxam), dodicin, N'- (2,5-Dimethyl-4-phenoxy-phenyl ) -N-ethyl-N-methyl-formamidine, N '- [4- (4,5-Dichloro-thiazol-2-yloxy) -2,5-dimethyl-phenyl] -N-ethyl-N-methyl-formamidine , N '- [4 - [[3- [(4-chlorophenyl) methyl] -1,2,4-thiadiazol-5-yl] oxy] -2,5-dimethyl-phenyl] -N-ethyl-N- methyl-formamidine, ethirimol, 3'-chloro-2-methoxy-N - [(3RS) -tetrahydro-2-oxofuran-3-
il] aceto-2 ', 6'-xylidide (clozilacone), cyprodinil, mepanipyrim, pyrimethanil, dithianone, aureofungin, blasticidin-S, biphenyl, chloronebe, dichlorane, hexachlorobenzene, quintozene, technazene, (TCNB), methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, tetra , 2,6-dichloro-N- (4-trifluoromethylbenzyl) -benzamide, fluopicolide (flupicolide), thioximide, flussulfamide, benomile, carbendazime, carbendazim hydrochloride, chlorphenazole, fuberidazole, thiabendazole, thiophanate, methanol, biazentia, triazine, methazine acibenzolar, betoxazine, pyriophenone (IKF-309), acibenzolar-S-methyl, pyribencarb (KIF-7767), butylamine, 3-iodo-2-propynyl n-butylcarbamate (TPBC), isopropanyl butylcarbamate (ioprocarpyl) butylcarbamate butylcarbamate (iodocarb) picarbutrazox, polycarbamate, propamocarb, tolprocarb, 3- (di fluoromethyl) -N- (7-fluoro-1,1,3,3-tetramethyl-indan-4-11) -l-methyl-pyrazole-4- carboxamide diclocimete, N- [(5-chloro-2-isopropyl-phenyl) methyl] -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-pyrazole-4-ca rboxamide, N-cyclopropyl-3- (di-fluoromethyl) -5-fluoro-N - [(2-isopropylphenyl) methyl] -1- methyl-pyrazolo-4-carboxamide carpropamide, chlorotalonyl, flumorfe, oxin-copper, cymoxanil, phenamacryl , cyzofamide, flutianyl, thicophene, clozolinate, iprodione, procymidone, vinclozoline, bupyrimide, dinoctone, dinopentone, dinobutone, dinocape, meptildinocape, diphenylamine, phosdiphen, 2,6-dimethyl- [1,4] diti-ino [2,3- c: 5,6-c '] dipyrrolo- 1,3,5,7 (2H, 6H) -tetraone, azithiram, eteme, ferbame,
mancozebe, manebe, metame, methram (polamame) methram-zinc, nabame, propineb, thiram, vapame (sodium metam), zineb, zirame, dithioether, isoprothiolane, etaboxam, fosetila, fosetila-Al (fosetila-al), bromide of al methyl, methyl iodide, methyl isothiocyanate, cyclamfuramide, fenfuram, validamycin, streptomycin, (2RS) -2-bromo-2- (bromomethyl) glutaronitrile (bromotalonyl), dodine, doguadine, guazatin, iminoctadine, iminoctadine 2, iminoctadine triacetate, 2 4-D, 2,4-DB, casugamycin, dimethyrimol, phenhexamide, himexazole, hydroxy-isoxazole imazalil, imazalyl sulfate, oxpoconazole, pefurazoate, prochloraz, triflumizole, phenamidone, Bordeaux mixture, calcium polysulfide, copper acetate , copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper oxyquinolate, copper silicate, copper sulfate, copper talate, cuprous oxide, sulfur, carbaryl, phthalide (phthalide), dingjunezuo (Jun Si Qi), oxatiapiproline, fluoroimide, mandipropamide , KSF-1002, benzamorph, dimetomorph, fenpropimorph, tridemorph, dodemorphe, dietofencarb, fentin acetate, fentin hydroxide, carboxine, oxycarboxine, drazoxolone, famoxadone, m-phenylphenol, p-phenylphenol, 2-tribromophenol (2), tribromophenol (2) - [(7,8-difluoro-2-methyl-3-quinolyl) oxy] -6-fluoro-phenyl] propan-2-ol, 2- [2-fluoro-6 - [(8-fluoro-2-methyl -3- quinolyl) oxy] phenyl] propan-2-o0ol cyflufenamide, ofurace, oxadixila, flutolanila, mepronila, isofetamida, fenpiclonila, fludioxonila, pencicurone, edifenfós, iprobenfós, pirazofósoft, phosphorus acids, keyboard,
captafol, captano, ditalinfós, triforina, fenpropidina, piperalina, ostol, l-methylcyclopropene, 4-CPA, clormequate, clofencete, diclorprope, dimetipina, endotal, etefona, flumetralina, forclorfenurone, gibberellic acid, mezzate, mezzate naphthalene acetamide, paclobutrazol, prohexadione, prohexadione-calcium, thidiazurone, tribuphos (tributyl phosphorotritioate), trinexapace, uniconazole, oao-naphthalene acetic acid, polyoxin D (polyoxime), BLAD, chitosan, phenoxanyl, foloxane, 3-phenoxanil (di-fluoromethyl) -N-methoxy-1-methyl-N- [11-methyl-2- (2,4,6-
trichlorophenyl) ethyl] pyrazole-4-carboxamide, bixafen, fluxpyroxade, furametpir, isopyrazame, penflufen, pentiopyrade, silkxane, phenpyrazamine, diclomezine, pyrifenox, boscalide, fluopyrame, diflumetorim, pyrimimidol-pyrimine-5-fluoro-pyrimimidol-pyrimimidol-pyrimimidol-pyrimidine-pyrimimidine-5-fluoro-pyrimidine-pyrimimidol-5-fluoro-pyrimidine-5-fluoro-pyrimidine. -4-amine ferinzone, dimethaclone (dimethaclone), pyroquinone, proquinazide, ethoxyquin, quinoxyphene, 4,4,5-trifluoro-3,3-dimethyl-1- (3-quinolyl) isoquinoline, 4,4-difluoro-3, 3-dimethyl-l1- (3-quinolyl) isoquinoline, 5-fluoro-3,3,4,4-tetramethyl-l1- (3-quinolyl) isoquinoline, 9-fluoro-2,2-dimethyl-5- (3 -quinolyl) -3H-1,4-benzoxazepine, tebufloquine, oxolinic acid, cinomethionate (oxytioquinox, quinoxymethate), spiroxamine, (E) -N- methyl-2- [2- (2,5-dimethylphenoxymethyl) phenyl] -2 -methoxyiminoacetamide, (mandestrobin), azoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, enoxastrobin phenamystrobin, fluphenoxystrobin, fluoxastrobin, cresoxime-methyl, mandestrobin, metaminostrobin, metominostrobin, orystrobin, orystrobin
picoxystrobin, pyraclostrobin, pyramethostrobin, piraoxystrobin, triclopyricarb, trifloxystrobin, amisulbrom, diclofluanide, tolylfluanide, N- [6 - [[(2) - [(1I-methylthetrazol-5-yl) -phenyl-methyl-methyl]]] -pyridyl] but-3-inyl carbamate, dazomet, isothianyl, thiadinyl, tifluzamide, bentiazole (TCMTB), siltiofam, zoxamide, anilazine, tricyclazole, (. + -.) - cis-l- (4-chlorophenyl) -2 - (1H-1,2,4-triazol-11-yl) -cycloheptanol (huanjunzuo), 1- (5S-bromo-2-pyridyl) -2- (2,4-difluorophenyl) -1,1- difluoro-3- (1,2,4-triazole-1-
il) propan-2-ol, 2- (1-tert-butyl) -1- (2-chlorophenyl) -3- (1,2,4-triazol-1-yl) -propan-2-ol (TCDP) , azaconazole, bitertanol (biloxazole), bromuconazole, climbazol, cyproconazole, diphenoconazole, dimetconazole, diniconazole, diniconazole-M, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, methanol, hexazol, methanol, hexazol, hexazol, hexane protioconazole, Mefentrifluconazole, simeconazole, tebuconazole, tetraconazole, triadimefone, triadimenol, triazoxide, triticonazole, 2 - [[(1R, 58) -5- [(4-fluorophenyl) methyl] -l1- hydroxy-2,2-dimethyl-cyclohexyl-2,2-dimethylopyl ] methyl] -4H-1,2,4-triazole-3-thione, 2 - [[3- (2-chlorophenyl) -2- (2,4-difluorophenyl) oxiran-2-yl] methyl] -4H- 1,2,4-triazol-3-thione, ametoctradine (imidium), iprovalicarb, valifenalate, 2-benzyl-4-chlorophenol (chlorophen), allyl alcohol, azafenidin, benzalkonium chloride, chloropicrin, cresol, daracide, dichlorophene (dichlorophene ), difenzoquate, dipyrithione, N-
(2-p-chlorobenzylethyl) hexamine, NNF-0721, octylin, oxasulfurone, propamidine and propionic acid; or an insecticide selected from abamectin, acephate, acetamipride, starch (S-1955), avermectin, azadiractin, azinphos-methyl, bifenthrin, biphenazate, buprofezine, carbofuran, cartap, chlorantraniliprol (DPX-E2Y45), chlorflaphyrone, chlorflapyrone -methyl, chromafenozide, clothianidin, cyflumetophen, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafentiurone, diazinone, dieldrin, diflubenzuron, dihydrogen, dihydrogen, dihydrogen, dihydrogen , phenothiocarb, phenoxycarb, fenpropatrin, fenvalerate, fipronil, flonicamide, flubendiamide, flucitrinate, tau-fluvalinate, flufenerime (UR-50701), flufenoxurone, fonofós, halofenozida, hexaflumurone, hydroxyphenone, hydroxyphenone, hydramethylone metalldehyde, metamidophos, methidathione, metomyl, methoprene, methoxychlor, metoflutrin, monocrotophos, methoxyfenozide, nitenp irame, nitiazine, novalurone, noviflumurone (XDE-007), oxamyl, parathione, parathione-methyl, permethrin, forato, fosalone, fosmete, phosfamidone, pirimicarb, profenofós, proflutrina, pimetrozina, pirafluprol, pyrethrin, pyrethrin, pyrethrin, pyrethrin, pyrethrin, pyrethrin, pyrethrin, pyrethrin, pyrethrin, pyrethrin, pyrethrin, pyrethrin, pyrethrin, pyrethrin, pyrethrin, pyrethrin, pyrethrin, pyrethyridine, pyrethyridine, pyrethyridine, pyrethyridine, pyrethyridine, pyrethyridine. , rotenone, rianodine, espinetorame, spinosad, spirodiclofen, spiromesifene (BSN 2060), spirotetramate, sulprofós, tebufenozide, teflubenzurone, teflutrina, terbufós, tetrachlorvinfós,
thiaclopride, thiamethoxam, thiodicarb, thiosultape-sodium, tralometrine, triazamate, trichlorone and triflumurone; or a bactericide selected from streptomycin; or an acaricide selected from amitraz, quinomethionate, chlorobenzylate, cyienopyraphene, ciexatin, dicofol, dienochlor, ethoxazole, phenazaquin, fenbutatin oxide, phenpropatrin, fenpyroximate, hexitiazox, propargite, pyridabene and tebufenpirade; or a biological agent selected from Bacillus thuringiensis, Bacillus thuringiensis delta-endotoxin, baculovirus and bacteria, viruses and entomopathogenic fungi.
[15]
Fungicidal composition according to any of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 and 14, characterized in that the composition additionally comprises an agriculturally acceptable vehicle and , optionally, a surfactant and / or formulation aids.
[16]
16. Method of control or prevention of phytopathogenic diseases, especially phytopathogenic fungi, in useful plants or in their propagation material, characterized by understanding the application to useful plants, their location or their propagation material of a fungicidal composition, as defined in any one of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and 15.
[17]
Method according to claim 16, characterized in that the components (A) and (B) of the composition are applied in a sequential manner.

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WO2022043576A2|2020-08-31|2022-03-03|Syngenta Crop Protection Ag|Pesticidally active heterocyclic derivatives with sulfur containing substituents|

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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EP17176062|2017-06-14|

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EP17176062.2|2017-06-14|

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PCT/EP2018/064949|WO2018228896A1|2017-06-14|2018-06-07|Fungicidal compositions|

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