巴西专利BR112014031279B1 synergistic compositions for the protection of agricultural crops and their use

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专利摘要:
SYNERGIC COMPOSITIONS FOR THE PROTECTION OF AGRICULTURAL CROPS AND THE USE OF THEM. Synergistic compositions comprising: a component (A), consisting of the compound having formula (I) 3-difluoromethyl-N- (7-fluoro-1,1,3-trimethyl-4indanyl) -1-methyl-4-pyrazole carboxamide one or more components (B) having a fungicidal or insecticidal activity, and its use for the control of harmful insects in agricultural crops.
公开号:BR112014031279B1
申请号:R112014031279-6
申请日:2013-06-13
公开日:2021-01-19
发明作者:Franco Pellacini；Matteo Santino Vazzola；Marilena Gusmeroli；Entela Sinani；Manuela Riservato
申请人:Stichting I-F Product Collaboration；
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[0001] The present invention relates to synergistic compositions for the protection of agricultural crops and their use.
[0002] In particular, the aim of the present invention is to provide compositions comprising a compound belonging to the chemical class of N-indanyl-pyrazole carboxamides and one or more fungicidal or insecticidal compounds.
[0003] In the application of antiparasitic products for use in agriculture, it is widely known to combine two or more products that have different mechanisms of action and / or a different biological target, in order to broaden the range of action of mixtures with respect to the product used individually and to prevent the occurrence of resistance phenomena from harmful organisms, phenomena that, over time, tend to reduce the effectiveness of the antiparasitic products used.
[0004] Compositions of N-indanyl-1-methyl-3- (halo) alkyl-4-pyrazole fungicidal carboxamides with fungicidal or insecticidal compounds, such as azoles, strobilurins, acylalanines, phenylpyrroles, chlorothalon, dithio carbamates, abamectin , insecticidal diamides, neonicotinoids, sulfoxaflor, pyrethroids, carbamates, phenylpyrazoles, are described in patent applications WO 2011/135833, WO 2011/135835, WO 2011/135836, WO 2011/135837, WO 2011/135838, WO 2011/135839, WO 2011/135827, WO 2011/135828, WO 2011/135830, WO 2011/135831, WO 2011/135832, WO 2011/135834, WO 2011/135840.
[0005] The applicant has now surprisingly found that with the combination of a specific fungicidal compound belonging to the class of N-indanyl-pyrazole carboxamides with one or more compounds selected from a series of compounds having fungicidal or insecticidal activity, compositions are obtained having biological activities that are: 1) improved over what is expected based on the activities of the products used alone; 2) superior to those that can be obtained with the compositions disclosed in the referred documents of the state of the art.
[0006] A first objective of the present invention, therefore, relates to synergistic compositions for the protection of agricultural crops comprising: - at least one component [A] consisting of the compound of formula (I) 3-difluoromethyl-N- (7-fluoro-1,1,3-trimethyl-4-indanyl) -1-methyl-4-pyrazole carboxamide
where Me represents a methyl group CH3-, - at least one component [B] selected from fungicidal or insecticidal compounds belonging to one or more of the following groups of fungicidal and insecticidal compounds:
[0007] Fungicidal compounds: i) azoles; ii) amino-derivatives; iii) strobilurins; iv) specific antioid compounds; v) aniline-pyrimidines; vi) benzimidazoles and the like; vii) dicarboximides; viii) polyhalogenated fungicides; ix) systemic acquired resistance (SAR) inducers; x) phenylpyrroles; xi) acylalanines; xii) antiperosporesic compounds; xiii) dithiocarbamates; xiv) arylamidines; xv) phosphorous acid and its derivatives; xvi) copper fungicidal compounds; xvii) fungicidal amides; xviii) nitrogen heterocycles; insecticidal compounds: xix) neonicotinoids; xx) phenylpyrazoles; xxi) pyrethroids; xxii) carbamates; xxiii) macrolides of microbial origin; xxiv) insecticidal diamides; xxv) trifluoromethylpyridyl derivatives.
[0008] The compound of formula (I) can be prepared: 1) by isomerization of N- (3-difluoromethyl-1-methyl-1H-4-pyrazol-carbonyl) - 6-fluoro-2,2,4- trimethyl-1,2,3,4-tetrahydro-quinoline (II), according to reaction scheme 1, and as described in Example 1: Scheme 1
2) by condensation of 3-difluoromethyl-1-methyl-1H-pyrazol-4-carboxylic acid or its derivatives, of the general formula (III), with 7-fluoro-1,1,3-trimethyl-4-aminoindane (IV ), using well-known methods in organic chemistry, according to scheme 2:
where X represents a selected group of OH, C1-C6 alkoxy or a halogen atom (preferably chlorine). The intermediate of formula (II) is, in turn, obtained by condensing a compound of general formula (III) with 6-fluoro-2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline ( V), according to scheme 3:
where X represents a group selected from OH, C1-C6 alkoxy or a halogen atom (preferably chlorine).
[0009] 3-Difluoromethyl-1-methyl-1H-pyrazol-4-carboxylic acid and its derivatives of general formula (III) are products described, for example, in US patent no. 5,093,347 known.
[0010] The intermediate of formula (V) can be prepared, according to reaction scheme 4, by hydrogenation of 6-fluoro-2,2,4-trimethyl-1,2-dihydroquinoline (VI), by in turn, obtained according to a method described in Organic Synthesis, Coll. Vol. III, p. 329, from acetone and 4-fluoroaniline: Scheme 4
in the mentioned formulas (I) - (VI), the symbol Me represents a methyl group CH3-.
[0011] The aminoindan of formula (IV) can be prepared analogously to that described in EP patent no. 065 4464, by condensation of 6-fluoro-2,2,4-trimethyl-1,2-dihydroquinoline (VI) with a carboxylic acid or its derivatives, hydrogenation in Pd / C, isomerization with sulfuric acid and hydrolysis of the bond amide with water in acetic acid.
[0012] The compound of formula (I) contains an asymmetric carbon atom at position 3 of the indanyl group and is generally obtained as a racemic mixture of the two enantiomers that have R and S configurations (molar ratio of R: S equal to 1: 1). However, it is possible to prepare mixtures of the two enantiomers of the compound of formula (I) in which the ratio of R: S is different from 1: 1 (enriched mixtures).
[0013] In addition, it is possible to prepare the unique R and S enantiomers of the compound of formula (I) in substantially pure form (> 99.99% by weight).
[0014] The aforementioned enriched enantiomeric mixtures and substantially pure single enantiomers can be prepared, for example, by condensing compounds of general formula (III) with enriched or enantiomerically pure forms (substantially pure unique enantiomers) of the general formula aminoindan ( IV), according to reaction scheme 2; enriched or enantiomerically pure forms of the aminoindane of formula (IV) can, in turn, be obtained through enantioselective and / or chemical reactions and / or chromatographic separation of the enantiomers, according to methods described in the literature for analogous products, for example , as disclosed in EP 0654464 mentioned above.
[0015] In the synergistic compositions of the present invention, the compound of formula (I) can be a racemic mixture, (I) -Rs, or an enriched mixture of one of the two enantiomers, or even a substantially pure (I) - specific enantiomer - R or (I) -S.

[0016] In the case of enriched mixtures of the compound of formula (I), those enriched in the R enantiomer are preferred, preferably with an R: S ratio of the two enantiomers ranging from 51:49 to 99.99: 0, 01 by weight.
[0017] Among the two enantiomeric forms of the compound of formula (I), the substantially pure isomer R is preferred.
[0018] The compounds from which component [B] of the synergistic compositions are selected are indicated here with their common international ISO name; their chemical structures and chemical names CAS and IUPAC are reported on Alan Wood's website (www.alanwood.net), Compendium of Pesticide Common Names; for most compounds, these characteristics are also reported, together with the physical-chemical data and biological characteristics, in “Pesticide Manual”, C.D.S. Tomlin, 15th Edition, 2009, British Crop Production Council Editor.
[0019] Examples of group xiv fungicidal arylamidines are reported in international patent applications WO 2000/46184, WO 2007/031508, and WO 2009/156098.
[0020] The preferred components [B] of the compositions object of the present invention are the following: i) azoles: azaconazole, bitertanol, bromuconazole, cyproconazole, diphenoconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, methazolazole, zazolazole, zazolazole, zazolazole, zazole , miclobutanil, penconazole, propiconazole, prochloraz, protioconazole, simeconazole, tebuconazole, tetra-itraconazole, triadimefon, triadimenol, triflumizole, triticonazole; ii) amino-derivatives: aldimorf, dodino, dodemorf, fen-propimorf, fenpropidin, guazatina, iminoctadina, spiroxamine, tridemorf; iii) strobiluris: azoxyestrobin, dimoxyestrobin, fluoxa-strobin, cresoxime-methyl, methinoestrobin, orisaestrobin, picoxyestrobin, pyracloestrobin, pyrameto-strobin, piraoxoestrobin, trifloxyestrobin; iv) specific antioid compounds: cyflufenamide, flutianyl, metrafenone, proquinazid, pyrophenone, quinoxyphene; v) aniline-pyrimidines: pyrimatanyl, mepanipyrim, cyprodinil; vi) benzimidazoles and analogues: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl; vii) dicarboximides: iprodione, procymidone; viii) polyhalogenated fungicides: chlorothalonil, captan, captafol, folpet, diclofluanid, tolylfluanid; ix) SAR inducers: acibenzolar, probenazole, isothianyl, thiadinyl; x) phenylpyrroles: fenpiclonil, fludioxonil; xi) acylalanines: benalaxyl, benalaxyl-M, furalaxil, metalaxyl, metalaxyl-M; xii) antiperosporesic compounds: ametoctradin, amisulbrom, bentiavalicarb, cyazofamide, cymoxanil, dimetomorf, etaboxama, famoxadone, fenamidone, flumetover, flumorf, fluopicolide, iprovalicarb, mandipropamide, valifenalate; xiii) dithiocarbamates: maneb, mancozeb, propineb, zineb; xiv) arylamidines: N-ethyl-N-methyl-N '- {4- [3- (4-chlorobenzyl) -1,2,4-thiadiazolyl-5-oxy] -2,5-xylyl} -formamidine; xv) phosphorous acid and derivatives: phosethyl aluminum, potassium phosphite, sodium phosphite, choline phosphite; xvi) copper fungicides: copper (II) hydroxide, copper oxychloride, copper (II) sulfate, Bordeaux mixture, copper salicylate C7H4O3 .Cu, cuprous oxide Cu2O; xvii) fungicidal amides: carpropamide, fenexamide, siltiofam, zoxamid, bixafen, boscalid, carboxin, fluopicolide, fluopirama, flutolanil, fluxpyroxad, furametpir, isopirasam, oxycarboxine, penflufen, pentiopirad, silkxide, tifluz; xviii) nitrogen heterocycles: fenpyrazamine, fluazinam, piribencarb, tebufloquin; xix) neonicotinoids: acetamipride, clothianidin, dinotefuran, flupiradifurone, imidacloprid, nitenpiram, insecticide, thiamethoxam; xx) phenylpyrazoles: etiprol, fipronil, flufiprol, pirafluprol, pyriprol; xxi) pyrethroids: bifenthrin, beta-cyfluthrin, lambda-cyhalothrin, cypermethrin, deltamethrin, teflutrin; xxii) carbamates: oxamil, tiodicarb, carbosulfan, metiocarb, carbofuran; xxiii) macrolides of microbial origin: abamectin, emamectin benzoate, espinetoram, spinosad; xxiv) insecticidal diamides: clorantraniliprol, cyantraniliprol, flubendiamide; xxv) trifluoromethylpyridyl derivatives: flonicamide, sulfoxaflor.
[0021] Among those mentioned above, the particularly preferred components [B] are the following: i) cyproconazole, diphenoconazole, epoxiconazole, flutriafol, penconazole, prochloraz, protioconazole, tebuconazole, tetraconazole; ii) fenpropimorf, spiroxamine; iii) azoxyestrobin, fluoxaestrobin, cresoxime-methyl, picoxyestrobin, pyracloestrobin, trifloxyestrobin; iv) metrafenone, proquinazid; v) mepanipirim, cyprodinil; vi) iprodione, procymidone; vii) carbendazim, thiophanate-methyl; viii) chlorothalonil; x) fludioxonil; xi) benalaxyl, benalaxyl-M, metalaxyl-M; xii) bentiavalicarb, cyazofamide, cymoxanil, dimetomorf, mandipropamide, valifenalate; xvi) copper (II) hydroxide, copper oxychloride, copper (II) sulfate, C7H4O3 copper salicylate Cu, Cu2O cuprous oxide; xix) clothianidin, imidacloprid, thiacloprid, thiamethoxam; xx) etiprol, fipronil; xxi) lambda-cyhalotrin, deltamethrin, teflutrin; xxiv) chlorantraniliprol, flubendiamide.
[0022] The weight ratios of components [A] and [B] in the compositions object of the present invention can vary within a wide range, even, depending on the parasites to be controlled and the single component [B] used (or the plurality) components [B] used), and are generally between 1:20 and 20: 1.
[0023] Preferred compositions are those comprising at least the following combinations of compounds: C1: (I) -RS + tetraconazole; C2: (I) -RS + tebuconazole; C3: (I) -RS + cyproconazole; C4: (I) -RS + diphenoconazole; C5: (I) -RS + epoxiconazole; C6: (I) -RS + flutriafol; C7: (I) -RS + penconazole; C8: (I) -RS + protioconazole; C9: (I) -RS + prochloraz; C10: (I) -RS + fenpropimorf; C11: (I) -RS + spiroxamine; C12: (I) -RS + azoxyestrobin; C13: (I) -RS + fluoxaestrobin; C14: (I) -RS + cresoxime-methyl; C15: (I) -RS + picoxyestrobin; C16: (I) -RS + pyracloestrobin; C17: (I) -RS + trifloxyestrobin; C18: (I) -RS + metrafenone; C19: (I) -RS + proquinazide; C20: (I) -RS + mepanipirima; C21: (I) -RS + cyprodinil; C22: (I) -RS + iprodione; C23: (I) -RS + procymidone; C24: (I) -RS + carbendazim; C25: (I) -RS + thiophanate-methyl; C26: (I) -RS + chlorothalonil; C27: (I) -RS + fludioxonil; C28: (I) -RS + benalaxyl-M; C29: (I) -RS + metalaxyl-M; C30: (I) -RS + bentiavalicarb; C31: (I) -RS + cyazofamide; C32: (I) -RS + cymoxanil; C33: (I) -RS + dimetomorf; C34: (I) -RS + mandipropamide; C35: (I) -RS + valiphenalate; C36: (I) -RS + copper salicylate C7H4O3 Cu; C37: (I) -RS + Cu2O cuprous oxide; C38: (I) -RS + clothianidin; C39: (I) -RS + imidacloprid; C40: (I) -RS + insecticide; C41: (I) -RS + thiamethoxam; C42: (I) -RS + etiprol; C43: (I) -RS + fipronil; C44: (I) -RS + lambda-cyhalothrin; C45: (I) -RS + deltamethrin; C46: (I) -RS + teflutrin; C47: (I) -RS + chloranthraniliprol; C48: (I) -RS + flubendiamide; C49: (I) -RS + tetraconazole + azoxyestrobin; C50: (I) -RS + tebuconazole + azoxyestrobin; C51: (I) -RS + epoxiconazole + azoxyestrobin; C52: (I) -RS + cyproconazole + azoxyestrobin; C53: (I) -RS + propiconazole + azoxyestrobin; C54: (I) -RS + protioconazole + azoxyestrobin; C55: (I) -RS + tetraconazole + picoxyestrobin; C56: (I) -RS + tebuconazole + picoxyestrobin; C57: (I) -RS + epoxiconazole + picoxyestrobin; C58: (I) -RS + cyproconazole + picoxyestrobin; C59: (I) -RS + propiconazole + picoxyestrobin; C60: (I) -RS + protioconazole + picoxyestrobin; C61: (I) -RS + tetraconazole + methyl cresoxim; C62: (I) -RS + tebuconazole + methyl cresoxim; C63: (I) -RS + epoxiconazole + methyl cresoxim; C64: (I) -RS + cyproconazole + methyl cresoxim; C65: (I) -RS + propiconazole + methyl cresoxim; C66: (I) -RS + protioconazole + methyl cresoxim; C67: (I) -RS + chlorothalonil + azoxyestrobin; C68: (I) -RS + chlorothalonil + picoxyestrobin; C69: (I) -RS + chlorothalonil + pyracloestrobin; C70: (I) -RS + chlorothalonil + methyl cresoxim; C71: (I) -RS + copper (II), copper hydroxide + oxychloride; C72: (I) -RS + copper (II) hydroxide, + copper oxychloride + C7H4O3 salicylate + Cu; C73: (I) -R8S2 + tetraconazole; C74: (I) - R8S2 + azoxyestrobin; C75: (I) - R8S2 + benalaxyl; C76: (I) -R9S1 + tetraconazole; C77: (I) -R9S1 + azoxyestrobin; C78: (I) -R + tetraconazole; where: - (I) -RS represents the compound of formula (I) in the form of a racemic mixture, - (I) -R8S2 represents the compound having the R and S enantiomers in the molar ratio of R: S = 8: 2, - (I) -R9S1 represents the compound having the R and S enantiomers in the molar ratio of R: S = 9: 1, - (I) -R represents the R enantiomer in substantially pure form (> 99.99% by weight) .
[0024] Preferably, in said compositions in C1-C25, C27-C35, C-38-C48 and C73-C77 the weight ratio of the components of [A] and [B] varies from 1:20 to 20: 1 .
[0025] Preferably, in said compositions in C26, C36, C37 the weight ratio of the components of [A] and [B] varies from 1:20 to 20:10.
[0026] Preferably, in said compositions in C49-C69 the weight ratio of the component of [A] with respect to two components [B] ([A]: [B1]: [B2]) varies from 1: 20:20 to 20: 1: 1.
[0027] Preferably, in said composition of C70 the weight ratio of component [A] with respect to the two components [B] ([A]: [B1]: [B2]) varies from 1:20:20 to 20: 10: 1, considering that in C71 the ratio of [A]: [B1]: [B2] varies from 1:20:20 to 20:10:10.
[0028] Preferably, in said composition C72, the weight ratio of component [A], with respect to the three components [B] ([A]: [B1]: [B2]: [B3]) varies from 1: 20:20:20 to 20: 10: 10: 10.
[0029] As already mentioned, the compositions object of the present invention exhibit a strong synergistic effect that can be evaluated through the application of Colby's formula ("Weeds", 1967, 15, p. 20-22.): Et = EA + EB- (EAXEB / 1 00) where Et is the percentage of expected effectiveness for the composition containing compounds A and B at dA + dB dosages, EA is the percentage of effectiveness observed for component A at dosage dA, EB is the percentage of effectiveness observed for component B at dB dosage.
[0030] When the observed effectiveness for the composition A + B (EA + B) is greater than the expected effectiveness according to the Colby formula (EA + B / Et> 1), there is no presence of a synergistic effect .
[0031] In the case of ternary combinations, Colby's formula becomes: Et = EA + EBI + EB2- (EA- EBI + EA'EB2 + EBI ■ EB2 / 1 00) + (EA- EBI ■ EBS / 1 0000)
[0032] where Et is the percentage of effectiveness expected for the composition containing compounds A, B1 and B2, at dosages dA + dB1 + dB2, AE represents the percentage efficay observed for component A at dosage dA, EB1 is the percentage of effectiveness observed for component B1 at dosage dB1, EB2 is the percentage of effectiveness observed for component B2 at dosage dB2. When the observed effectiveness for the composition A + B1 + B2 (EA + B1 + B2) is greater than the expected effectiveness according to Colby's formula (EA + B1 + B2 / Et> 1), there is no presence of synergistic effect.
[0033] Due to the high synergistic effects, the amplitude of the action range, the considerable reduction in the resistance phenomena of the target microorganisms, the compositions object of the present invention are endowed with a very high fungicidal activity, which is exerted in what concerns numerous phytopathogenic fungi attacking important agricultural crops.
[0034] The said compositions have a fungicidal activity that can be curative, preventive or eradication, and generally have very low or zero phytotoxicity on the treated cultures.
[0035] It is, therefore, another objective of the present invention to use the synergistic fungicidal compositions previously described for the control of phytopathogenic fungi in agricultural crops.
[0036] Examples of pathogenic fungi that can be effectively treated and sustained with the compositions of the present invention are those belonging to the groups of Basidiomycetes, Ascomycetes, Deuteromycetes or imperfect fungi, Oomycetes: Puccinia spp., Ustilago spp., Tilletia spp., Uromyces spp., Phakopsora spp., Rhizoctonia spp., Erysiphe spp., Sphaerotheca spp., Podosphaera spp., Uncinula spp., Helminthosporium spp., Rhynchosporium spp., Pyrenophora spp., Monilinia spp., Sclerotinia spp. (Mycosphaerella spp.), Venturia spp., Botrytis spp., Alternaria spp., Fusarium spp., Cercospora spp., Cercosporella herpotrichoides, Colletotrichum spp., Pyricularia oryzae, Sclerotium spp., Phytophtora spp., Pythium spp. , Peronospora spp., Pseudoperonospora cubensis, Bremia lactucae.
[0037] The main crops that can be protected with the compositions according to the present invention include cereals (wheat, barley, rye, oats, rice, corn, sorghum, etc.), fruit trees (apples, pears, plums, peaches, almonds, cherries, bananas, grapes, strawberries, raspberries, blackberries, etc.), citrus trees (oranges, lemons, tangerines, grapefruits, etc.), vegetables (beans, peas, lentils, soybeans, etc.), vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, eggplants, peppers, etc.), cucurbits (pumpkins, zucchini, cucumbers, melons, watermelons, etc.), oilseeds (sunflower, rapeseed, peanuts, castor beans , coconut, etc.), tobacco, coffee, tea, cocoa, sugar beet, sugar cane, cotton.
[0038] In particular, the compositions of the present invention have proved to be particularly effective in controlling Plasmopara viticola in vines, Phytophtora infestans and Botrytis cinerea in tomatoes, Puccinia recondita, Erysiphae graminis, Helminthosporium teres, Septoria nodorum and Fusarium spp. in cereals, in the control of Phakopsora pachyrhizi in soybeans, in the control of Uromyces appendiculatus in beans, in the control of Venturia inaequalis in apple trees, in the control of Sphaerotheca fuliginea in cucumbers.
[0039] In addition, the compositions of the present invention are also effective in controlling phytopathogenic bacteria and viruses, such as, for example, Xanthomonas spp., Pseudomonas spp., Erwinia amylovora, the tobacco mosaic virus.
[0040] Compositions comprising at least one compound of formula (I) and, as component [B], at least one insecticidal compound selected from one or more of said groups of compounds xix-xxv, in addition to having excellent fungicidal activity , also have an excellent insecticidal activity against numerous species of insects harmful to agricultural crops.
It is, therefore, another object of the present invention to use said compositions, comprising at least one compound of formula (I) and at least one insecticidal compound selected from or more of said groups of compounds xix-xxv mentioned above, for the control of harmful insects in agricultural crops.
[0042] Examples of insects that can be controlled with the above compositions are those belonging to the order of Hemipthera, Lepidopthera, Tysanopthera, Dipthera, Coleopthera, Orthopthera, Hymenopthera: Aphis gossypii, Myzus persicae, Macrosiphum euphorbiae, Brevic , Trialeurodes vaporariorum, Bemisia tabaci, Aonidiella aurantii, Comstockaspis perniciosa, Unaspis citri, Psylla piri, Laodelphax striatellus, Nilaparvata lugens, Nephotettix cincticeps, Nephotettix virescens, Chilo suppressalis, Ostrinia spp. spp., Heliothis spp., Helicoverpa spp., Pieris spp., Adoxophyes spp., Grapholita molesta, Cydia spp., Phyllonorycter blancardella, Lymantria spp., Plutella xylostella, Pectinophora gossypiella, Hyphantria cunea, Spipspini. Dacus spp., Ceratitis capitata, Liriomyza trifolii, Anthonomus grandis, Callosobruchus chinensis, Diabrotica spp., Agriotes spp., Tribe lium spp., Locusta migratoria, Oxya spp., Solenopsis spp., Blattella germanica, Periplaneta spp ..
[0043] Even though the components [A] and [B] can be mixed and applied as such on the crops to be protected, for practical use in agriculture, it is generally preferable to use the fungicidal compositions according to the present invention, in the form of suitable phytosanitary formulations.
[0044] Component [A] and components [B] can be formulated separately and mixed in the pre-selected diluent (for example, water) when treating the crops to be protected, or combined together in the ready-made single formulation for use before treatment.
[0045] Both in the case of components formulated separately, and in the case of components [A] and [B] combined together in ready-to-use formulations, the formulations can be in the form of dry powders, wet powders, emulsifiable concentrates, emulsions, microemulsions, pastes, granules, water-dispersible granules, solutions, suspensions, etc .: the selection of the formulation type depends on the characteristics of components A and B, and the specific use.
[0046] The compositions are prepared with known methods, for example, by diluting the active ingredients with a solid or liquid diluent, possibly in the presence of surfactants, dispersants, suspending agents, stabilizers, adjuvants, etc.
[0047] The following can be used, for example, as solid or carrier diluents: silica, kaolin, bentonite, talc, diatomaceous earth, dolomite, calcium carbonate, magnesia, plaster, clays, synthetic silicates, atapulgite, sepiolites.
[0048] The following can be used, for example, as solvents or liquid diluents, in addition to water, aromatic organic solvents (mixtures of xylols or alkylbenzols, chlorobenzene, etc.), paraffins (oil fractions), alcohols (methanol, propanol, butanol, octanol, glycerol, etc.), esters (ethyl acetate, isobutyl acetate, alkyl carbonates, adipic acid alkyl esters, glutaric acid alkyl esters, succinic acid alkyl esters, alkyl esters lactic acid, etc.), vegetable oils (rapeseed oil, sunflower oil, soy oil, castor oil, corn oil, peanut oil, and their alkyl esters), ketones (cyclohexanone, acetone, acetophenone, isophorone, ethyl amyl ketone, etc.), amides (N, N-dimethylformamide, N-methylpyrrolidone, etc.), sulfoxides and sulfones (dimethylsulfoxide, dimethylsulfone, etc.) and mixtures thereof.
[0049] The surfactants that can be used are sodium salts, calcium salts, potassium salts, triethylamine or alkyl naphthalene sulfonates, polynaphthalene sulfonates, alkyl sulfonates, aryl sulfonates, alkyl aryl sulfonates, polycarboxylates, sulfosuccinates, alkyl sulfosuccinates lignin sulfonates, alkyl sulfates; and again polyethoxylated fatty alcohols, polyethoxylated alkyl phenols, polyethoxylated sorbitol esters, polyethoxylated polypropoxy (block copolymers), can be used.
[0050] The compositions may also contain special additives for particular purposes, for example, antifreeze agents, such as propylene glycol, or adhesives, such as gum arabic, polyvinyl alcohol, polyvinylpyrrolidone, etc.
[0051] If desired, other active ingredients compatible with [A] and [B] can be added to the compositions, such as, for example, other fungicidal or insecticidal compounds other than the components [B] described above, phytoregulators, antibiotics, herbicides, fertilizers and / or mixtures thereof.
[0052] Examples of fungicides other than components [B], which can be included in the synergistic compositions object of the present invention are listed below with their international name ISO: ampropylphos, anilazine, benodanil, blasticidin-S, bupirimate, butiobate, quinomethionate , cloroneb, clozolinato, debacarb, diclone, diclobutrazol, diclomezine, dicloran, diclocimet, dietofencarb, diflumetorim, dimethyrimol, dinocap, dipyrithione, ditalimphos, dithianone, edifenfos, etirimol, phenoxy, phenoxy, phenoxy, phenoxy, phenoxy, phenoxy, phenoxy, phenoxy, phenoxy , ferbam, ferimzone, fluoroimide, fluotrimazole, flusulfamide, himexazole, hydroxyquinoline sulphate, iprobenfos, isoprothiolane, casugamycin, mancobre, mebenil, mepronil, meptildinocap, metfuroxam, metiram, methoxyl, isoxyxyl, natamic, methoxyl, oxamic, natamin , pefurazoate, pencicuron, pentachlorophenol and its salts, phthalide, piperalin, polyoxins, propamocarb, protiocarb, piracarbolid, pyrazophos, pyribenc arb, pirifenox, piroquilone, piroxifur, quinacetol, quinazamid, quintozene, streptomycin, thiadifluor, ticiofen, tiram, thioximid, tolclofos-methyl, triarimol, triazbutyl, triazoxide, tricyzoline, triforoline, validacyzine, zincamine
[0053] The total concentration of components [A] and [B] in said compositions can vary within a wide range; which generally ranges from 1% to 99% by weight relative to the total weight of the composition, preferably between 5% and 90% by weight relative to the total weight of the composition.
[0054] In order to protect agricultural crops, the compositions object of the present invention can be applied to any part of the plant, or on the seeds before sowing, or on the soil in which the plant grows.
[0055] Another object of the present invention, therefore, relates to a method for the control of phytopathogenic fungi in agricultural crops, which comprises the application of an effective dose of at least one synergistic fungicidal composition of the type described above, on one or more parts of the plant to be protected (for example, on seedlings, leaves, fruits, stems, branches, roots) and / or on the seeds of the said plants before sowing, and / or on the soil in which the plant grow up.
[0056] Another aspect of the present invention is a method for the control of harmful insects in agricultural crops, which comprises the application of an effective dose of at least one synergistic fungicidal composition comprising at least one compound of formula (I) and at least one insecticidal compound selected from one or more of the groups of compounds xix-xxv described above, in one or more parts of the plant to be protected (for example, on seedlings, leaves, fruits, stems, branches, roots) and / or on the seeds of said plants before sowing, and / or on the soil on which the plant grows.
[0057] The preferred form of application for compositions comprising compound (I) and at least one insecticidal compound selected from one or more groups of compounds xix-xxv is the treatment of seeds (seeddressing).
[0058] The total amount of components of [A] and [B] to be applied in order to obtain the desired effect can vary according to different factors, such as, for example, the compounds used, the culture to be preserved, the type of pathogen or insect, the degree of infection, the climatic conditions, the method of application, the formulation used.
[0059] Total doses of components [A] and [B] ranging from 10 g to 5 kg per hectare of agricultural crop generally provide sufficient control.
[0060] The following examples are provided for a better understanding of the invention, which should be considered to be illustrative and not to limit it. EXAMPLE 1
[0061] Preparation of 3-difluoromethyl-N- (7-fluoro-1,1,3-trimethyl-4-indanyl) -1-methyl-4-pyrazole carboxamide (I)
[0062] A 40 g solution of 3- (difluoromethyl) -1-methyl-1H-pyrazol-4-carbonyl [compound of formula (III); PM 194.5], in 40 ml of dichloroethane, is dripped at room temperature in a solution of 34 g of 6-fluoro-2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline [composed of formula (V); PM 193] and 30 ml of triethylamine in 200 ml of dichloroethane.
[0063] After stirring for 3 hours at reflux, the reaction mixture is poured into water (1.2 l) and extracted with dichloroethane. The organic layer is washed with 10% aqueous hydrochloric acid, made anhydrous with sodium sulfate, concentrated in vacuo to obtain 58 g of a crude solid product which corresponds to N- (3-difluoromethyl-1-methyl-1H- 4-pyrazol-carbonyl) -6-fluoro-2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline [compound of formula (II); CG-mass: M + = 351].
[0064] For this crude product, 165 ml of 85% aqueous sulfuric acid is added and the mixture is then heated under stirring at 60 ° C for 30 minutes. After cooling the mixture is poured into water and ice, and extracted with dichloromethane. The organic layer is then washed with water, with a saturated solution of sodium bicarbonate in water, and with a saturated solution of sodium chloride in water. The organic layer is dried over sodium sulfate and concentrated in vacuo: the residue is purified by chromatography on silica gel (eluent heptane / EtOAc 6: 4) to produce 48 g of a white solid with a melting point of 147 ° C, which corresponds to the desired product in racemic form, (I) -RS. CG- mass: M + = 351.
[0065] 1H NMR (200 MHz, CDCl3) at: 1.43 (3H, d), 1.38 (3H, s), 1.44 (3H, s), 1.66 (1H, dd), 2 , 21 (1H, dd), 3.38 (1H, m), 3.98 (3H, s), 6.81 (1H, bs), 6.95 (1H, t), 6.70. (1H, m), 7.81 (1H, bs), 8.03 (1H, bs) EXAMPLE 2
[0066] Preparation of enantiomers separated from compound (I).
[0067] 36.8 g (1 eq) of racemic 7-fluoro-1,1,3-trimethyl-4-aminoindane [compound (IV)] and 14.3 g (0.5 eq) of D- ( 2S, 3S) - (-) - tartaric methanol (30 ml) were mixed and heated to 70 ° C for 1 hour.
[0068] The mixture was allowed to cool to room temperature; a precipitate was formed and the mixture was kept overnight at 4 ° C. The formed solid was filtered, washed with a small amount of methanol and recrystallized from methanol six times to produce 14.8 g of an off-white solid, which corresponds to 7-fluoro-1,1,3- D-tartrate trimethyl-4-aminoindane.
[0069] For the salt, a 5% aqueous sodium hydroxide solution was added to pH 10, and the mixture was extracted three times with diethyl ether. The combined organic layers were washed with water and brine. Then, they were dried over Na2SO4 and concentrated under reduced pressure to obtain 6.38 g of (-) - 4-amino-7-fluoro-1,1,3-trimethylindane as a white powder (17% yield); and is. > 99% (HPLC).
[0070] For a 600 mg solution of 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid [compound (III)] and a catalytic amount of N, N-dimethylformamide in dichloromethane (7 mL), 450 mg of thionyl chloride were added dropwise. The mixture was refluxed for 2 h. The reaction was monitored by GC / MS. The solvent was evaporated in vacuo. The obtained crude acid chloride was used in the next step.
[0071] A solution of the crude product of 3-difluoromethyl-1-methyl-1H-pyrazol-4-carbonyl in dichloroethane (6 mL) was added dropwise over a period of 10 minutes, under a nitrogen atmosphere, to a solution of 660 mg of (-) - 4-amino-7-fluoro-1,1,3-trimethylindane, a catalytic amount of 4-dimethylaminopyridine and 420 mg of triethylamine in dichloroethane (5 ml).
[0072] The mixture was stirred at room temperature overnight. At the conclusion of the reaction (monitored by GC-MS), the mixture was diluted with dichloromethane (20 ml) and cooled to 0 ° C; a solution (20 mL) of 5% HCl was added.
[0073] The layers were separated and the organic phase was washed with 5% HCl solution (2 x 20 ml), water (2 x 20 ml) and brine, then dried over Na2SO4. The solvent was evaporated under reduced pressure to produce 1.3 g of a pale yellow solid.
[0074] The crude product was purified by column chromatography (eluent: heptane / EtOAc 6: 4) to yield 1.1 g (92% yield) of 99.5% pure (-) enantiomer (ee> 99% determined by HPLC with chiral column) as a solid white with mp = 129-130 ° C.
[0075] GC-MS: M + = 351; [] D20 = - 59.5 ° (CHCl3, 1 g / 100 ml).
[0076] Similarly, starting from racemic 7-fluoro-1,1,3-trimethyl-4-aminoindan [compound (IV)] and L- (2R, 3R) - (+) - tartaric acid, 99 , 3% pure (+) enantiomer, was prepared (ee> 99%, determined by HPLC with chiral column): white solid with mp = 131-132 ° C.
[0077] GC-MS: M + = 351; [] D20 = + 60.1 ° (CHCl3, 1 g / 100 ml). EXAMPLE 3
[0078] Determination of the "in vitro" activities of racemic (I) and enantiomers against phytopathogenic microorganisms.
[0079] Under sterile conditions, the racemic technician (I), the enantiomers (-) and (+) (prepared in Example 2) under the test, were dissolved in dimethylsulfoxide and diluted in series three times to obtain an inhibition curve of growth. The aqueous treatment solutions were prepared by adding stocks of DMSO to water and mixing by pipette resulting in a final treatment concentration 2x and a final concentration of DMSO 2x of 1.6%.
[0080] The sporulation plates of phytopathogenic microorganisms were harvested under sterile conditions in Potato Dextrose Broth with 1/2 force. The spores were removed by filtration and diluted with gauze and about 40,000 spores per ml. The spores were aliquoted in 96-well microtiter plates at 150 microliters of spore suspension per well. The pathogenic spore suspensions were then treated with the 2x aqueous treatment solution or 1.6% DMSO for the controls to produce a final concentration of 1x or 0.8% DMSO. The plates were then kept for 43 hours at room temperature.
[0081] After 43 hours at room temperature, the plates were visually evaluated microscopically for spore germination and growth inhibition. The plates were also quantitatively measured for growth inhibition by measuring the optical density in a 405 nanometer wavelength spectrophotometric plate reader. The optical density was corrected for the absorbance of the medium and the active ingredient by subtracting the readings at 405 nm for the 2x treatment aqueous solution or DMSO solution diluted with 1/2 force POTATO DEXTROSE BREAST and without spores.
[0082] The% inhibition of pathogen growth obtained for the technical racemic (I), enantiomers (-) and (+) was calculated according to the formula:
[0083] Inhibition Percentage = ((1 - (OD trt - OD trt white) / (OD without treatment - OD white without treatment)) x 100)
[0084] where OD trt is the optical density at 405 nm for the spore suspension plus the aqueous treatment solution and the OD trt in white is the optical density at 405 nm for the aqueous treatment solution 2x plus DEXTROSE DEAL POTATO with 1/2 force and without spores and OD without treatment is the optical density at 405 nm for DMSO at 1.6% and OD without treatment at white is the optical density at 405 nm for DMSO of 1.6%, more POTATO DEXTROSE BREAST with 1/2 force and without spores. Values are the average of three replicates. The concentrations of racemic, enantiomers (-) and (+), which produce 50% growth inhibition (pI50) were calculated using the GraphPad Prism software. The percentage inhibition values were calculated using the GraphPad Prism Version 4 software.
[0085] The microorganisms tested were Botrytis cinerea (BC), Stagonospora nodorum (SN) and Magnaporthe griseae (MG).
[0086] The results are shown in Table 1.
NI = No inhibition EXAMPLE 4
[0087] Determination of the fungicidal activity in the preventive application (5 days) against Puccinia recondita in wheat.
[0088] Leaves of wheat plants of the variety Salgemma, grown in pots in a conditioned environment maintained at 20 ° C and 70% relative humidity (RH), were treated by spraying on both sides of the leaves with the compounds and compositions under test, dispersed in 20% by volume acetone hydroacetonic solutions.
[0089] After staying for 5 days in a conditioned environment, the plants were sprayed on both sides of the leaves with an aqueous conidia suspension of Puccinia recondita (2 mg of inoculum per 1 ml of solution for infection).
[0090] After being sprinkled, the plants were kept in an environment saturated with humidity, at a temperature ranging from 18 to 24 ° C during the incubation period of the fungus (1 day).
[0091] After this period, the plants were placed in a greenhouse with 70% U.R. and at a temperature of 18-24 ° C for 14 days.
[0092] At the end of this period, the external symptoms of the pathogen appeared and, therefore, it was possible to proceed to a visual assessment of the intensity of the infection. The fungicidal activity was expressed as a percentage of reduction of the affected leaf areas with respect to untreated plants used as controls: the scale comprised, as extremes, the value 100 (total activity; healthy plant) and the value of 0 (no activity; completely infected plants).
[0093] At the same time, the phytotoxicity (percentage of leaf necrosis) induced in wheat plants from the application of the products and compositions was evaluated: in this case, the scale ranges from 0 (no phytotoxicity) to 100 (completely necrotic plant) .
[0094] In Table 2, the activities of the racemic (I) and the pure enantiomers of compound (I), prepared in Example 2, are reported.

[0095] The synergism of the compositions (A + B) under test was evaluated according to the Colby formula: Et = EA + EB- (EAXEB / 1 00) where Et is the expected percentage of effectiveness for the composition containing the compounds A and B, in dosages dA + dB, EA is the percentage of effectiveness observed for component A in dosage dA, EB is the percentage of effectiveness observed for component B in dosage dB.
[0096] When the observed effectiveness for the composition A + B (EA + B) is greater than the expected effectiveness according to the Colby formula (EA + B / Et> 1), a synergistic effect is confirmed. EXAMPLE 5
[0097] Determination of synergistic effects "in vitro" against phytopathogenic microorganisms.
[0098] Under sterile conditions, the products and compositions under test were dissolved in dimethylsulfoxide, diluted with water and added under vigorous stirring to POTATO DEXTROSE AGAR, maintained in a thermostatic bath at 55 ° C. The AGAR preparations containing the compounds and test compositions under the desired rates, were poured into Petri dishes of 60 mm in diameter (three for each product and composition) and allowed to cool to room temperature.
[0099] After solidification of the medium with Agar, the AGAR discs having a diameter of 6 mm and supporting the mycelium of the microorganism, were placed in the center of the Petri dishes; Petri dishes containing untreated POTATO DEXTROSE AGAR were also inoculated with the microorganism and used as a control.
[00100] After incubation at 28 ° C, when the control colonies had grown more than 30 mm in diameter, but without reaching the edge of the plates, the diameters of the colonies developed on treated and untreated plates were measured; the percentage of growth inhibition of the microorganism obtained with products and compositions was calculated according to the formula: I = (1 - Zi / Zo) x 100 where Z1 is the diameter (average of three replicates) of the colonies treated with compounds and mixtures and Z0 is the diameter (average of three replicates) of untreated colonies.
[00101] The microorganisms tested were Botrytis cinerea, Fusarium culmorum, Helminthosporium teres, Pyricularia oryzae, Septoria nodorum, Venturia inaequalis.
[00102] The synergism of a binary mixture (A + B) with the dose (dA + dB) was evaluated according to Colby's formula: It = IA + IB - (IAXIB / 100) where:
[00103] It is the% growth inhibition expected for the mixture; IA is the% growth inhibition observed for compound A at dose dA; IB is the% growth inhibition observed for compound B at a dB dose.
[00104] When the% growth inhibition observed for the composition (A + B) is greater than that calculated by Colby's formula a (IA + B> It; IA + B / It> 1), a synergistic effect is confirmed.

权利要求:
Claims (10)
[0001]
1. Synergistic compositions for the protection of agricultural crops, characterized by the fact that they comprise: - component (A), which consists of the compound having the formula (I) 3-difluoromethyl-N- (7-fluoro-1,1,3- trimethyl-4-indanyl) -1-methyl-4-pyrazole carboxamide
[0002]
2. Synergistic compositions according to claim 1, characterized by the fact that said compound having the formula (I) is a racemic mixture ((I) -RS).
[0003]
Synergistic compositions according to either of claims 1 or 2, characterized in that said compound having formula (I) is selected from: - a mixture enriched in one of the enantiomers, preferably a mixture enriched in the R enantiomer, - one of the two R ((I) -R) or S ((I) -S) enantiomers in a substantially pure form (> 99.99% by weight), preferably the R enantiomer.
[0004]
Synergistic compositions according to any one of claims 1 to 3, characterized by the fact that the weight ratio between said component [A] and said component [B] varies from 1:20 to 20: 1.
[0005]
5. Synergistic compositions according to any one of claims 1 to 4, characterized by the fact that they are selected from among: C1: (I) -RS + tetraconazole; C4: (I) -RS + diphenoconazole; C8: (I) -RS + protioconazole; C11: (I) -RS + spiroxamine; C12: (I) -RS + azoxyestrobin; C13: (I) -RS + fluoxaestrobin; C14: (I) -RS + cresoxime-methyl; C16: (I) -RS + pyracloestrobin; C18: (I) -RS + iprodione; C22: (I) -RS + chlorothalonil; C30: (I) -RS + valifenalate; C34: (I) -RS + imidacloprid; C73: (I) + -R8S2 tetraconazole; C74: (I) + -R8S2 azoxyestrobin; C75: (I) + -R8S2 benalaxyl; C76: (I) + -R9S1 tetraconazole; C77: (I) + -R9S1 azoxyestrobin; C78: (I) -R + tetraconazole; where: - (I) -RS indicates the compound having formula (I) in the form of a racemic mixture, - (I) -R8S2 indicates the compound containing the R and S enantiomers in a molar ratio of R: S = 8: 2, - (I) -R9S1 indicates the compound containing the R and S enantiomers in a molar ratio of R: S = 9: 1, - (I) -R indicates the R enantiomer in substantially pure form (> 99 , 99% by weight).
[0006]
Synergistic compositions according to any one of claims 1 to 5, characterized in that said component [A] and said component [B] are diluted with one or more solid or liquid diluents, possibly with the addition of one or more surfactants, dispersing agents, suspending agents, stabilizers, adjuvants, antifreeze agents, adhesion agents.
[0007]
7. Use of synergistic compositions as defined in any of claims 1 to 6, characterized by the fact that it is for the control of phytopathogenic fungi in agricultural crops.
[0008]
8. Use of synergistic compositions according to claim 7, characterized by the fact that it is for the control of phytopathogenic fungi selected from the following groups: Basidiomycetes, Ascomycetes, Deuteromycetes or imperfect fungi, Oomycetes: Puccinia spp., Ustilago spp., Tilletia spp., Uromyces spp., Phakopsora spp., Rhizoctonia spp., Erysiphe spp., Sphaerotheca spp., Podosphaera spp., Uncinula spp., Helminthosporium spp., Rhynchosporium spp., Pyrenophora spp., Monilinia spp., Monilinia spp. , Septoria spp. (Mycosphaerella spp.), Venturia spp., Botrytis spp., Alternaria spp., Fusarium spp., Cercospora spp., Cercosporella herpotrichoides, Colletotrichum spp., Pyricularia oryzae, Sclerotium spp., Phytophtora spp., Pythium spp. , Peronospora spp., Pseudoperonospora cubensis, Bremia lactucae.
[0009]
9. Use of synergistic compositions according to claim 7 or 8, characterized by the fact that agrarian crops are selected from: cereals, fruit trees, citrus fruits, vegetables, vegetable crops, pumpkins, oilseeds, tobacco, coffee, tea, cocoa, sugar beet, sugar cane, cotton.
[0010]
10. Method for controlling phytopathogenic fungi in agricultural crops, characterized by the fact that it comprises the application of an effective dose of at least one composition as defined in any of claims 1 to 6, in one or more parts of the plants to protect them and / or on the seeds of said plants before sowing and / or on the soil on which said plants grow.

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同族专利:

公开号 | 公开日

DK2861067T3|2021-02-22|

AR091445A1|2015-02-04|

SI2861067T1|2021-08-31|

US10143200B2|2018-12-04|

CN104602523B|2017-12-15|

HUE053853T2|2021-07-28|

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PT2861067T|2021-02-24|

ITMI20121045A1|2013-12-16|

AU2016273956B2|2019-02-28|

PE20150177A1|2015-02-23|

AU2016273956A1|2017-01-12|

EP2861067B1|2020-12-02|

ZA201500035B|2017-06-28|

JP6215316B2|2017-10-18|

EA026484B1|2017-04-28|

US20190059376A1|2019-02-28|

ECSP15001325A|2015-09-30|

CA2875726C|2021-11-30|

UA116211C2|2018-02-26|

BR112014031279A2|2017-06-27|

AU2013276511B2|2017-01-19|

KR102035371B1|2019-10-22|

CN104602523A|2015-05-06|

PH12014502717A1|2015-02-02|

PH12014502717B1|2015-02-02|

JP2015519384A|2015-07-09|

MX363185B|2019-03-13|

ES2856198T3|2021-09-27|

WO2013186325A1|2013-12-19|

EA201492232A1|2015-08-31|

MX2014015427A|2015-03-05|

PL2861067T3|2021-08-23|

IL236227D0|2015-02-01|

KR20150023623A|2015-03-05|

EP2861067A1|2015-04-22|

TWI581711B|2017-05-11|

TW201410151A|2014-03-16|

CA2875726A1|2013-12-19|

US20150164076A1|2015-06-18|

CL2014003357A1|2015-02-27|

LT2861067T|2021-05-25|

AU2013276511A1|2015-02-05|

EP3788875A1|2021-03-10|

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法律状态:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |

2019-04-09| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

2020-04-07| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

2020-11-10| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

2021-01-19| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/06/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

申请号 | 申请日 | 专利标题

IT001045A|ITMI20121045A1|2012-06-15|2012-06-15|SYNERGIC COMPOSITIONS FOR THE PROTECTION OF AGRICULTURAL CROPS AND ITS USE|

ITMI2012A001045|2012-06-15|

PCT/EP2013/062306|WO2013186325A1|2012-06-15|2013-06-13|Synergistic compositions for the protection of agrarian crops and the use thereof|

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