WO2015121802A1 - Benzoylphényl-formamidines ayant une activité fongicide, leurs compositions agronomiques et leur utilisation - Google Patents

Benzoylphényl-formamidines ayant une activité fongicide, leurs compositions agronomiques et leur utilisation Download PDF

Info

Publication number
WO2015121802A1
WO2015121802A1 PCT/IB2015/051019 IB2015051019W WO2015121802A1 WO 2015121802 A1 WO2015121802 A1 WO 2015121802A1 IB 2015051019 W IB2015051019 W IB 2015051019W WO 2015121802 A1 WO2015121802 A1 WO 2015121802A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
methyl
group
compounds
general formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IB2015/051019
Other languages
English (en)
Inventor
Silvia Mormile
Paolo Bravini
Marilena Gusmeroli
Matteo Santino Vazzola
Lucio Filippini
Franco Pellacini
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Isagro SpA
Original Assignee
Isagro SpA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Isagro SpA filed Critical Isagro SpA
Publication of WO2015121802A1 publication Critical patent/WO2015121802A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/52—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing groups, e.g. carboxylic acid amidines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/44—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom three- or four-membered rings

Definitions

  • the present invention relates to phenylamidines having a high fungicidal activity; in particular, it relates to benzoylphenyl-formamidines having a high fungicidal activity and their use for the control of phytopathogenic fungi of important agricultural crops.
  • Arylamidines with a fungicidal activity are already known and are described, in particular, in international patent application WO 2000/46184.
  • N,N-dimethyl-N'-[4-(3-trifluoromethylbenzoyl)-2,5- xylyl-form-amidine (compound n. 398, Tab. 1, page 47) is exemplified.
  • a first object of the present invention therefore relates to new benzoylphenyl- formamidines having general formula (I):
  • Ri represents a C2-C6 alkyl, a C3-C6 cycloalkyl or a C4-C7 cycloalkylalkyl;
  • R2 represents a Ci-C alkyl
  • Ri and R 2 together with the N atom to which they are bound, form a heterocyclic ring containing from 4 to 7 atoms, possibly substituted by halogen atoms;
  • R3 and R4 equal to or different from each other, represent a hydrogen atom, a halogen atom, a C1-C6 alkyl, a C1-C6 alkoxyl, a C1-C6 haloalkoxyl, a CF 3 group, a CF 2 H group, a CFH 2 group or a cyano group;
  • R equal or different when n > 2, represents a halogen atom, a C 1 -C4 alkyl group, a C 1 -C4 haloalkyl group, a C 1 -C 4 alkoxyl group, a C 1 -C 4 haloalkoxyl group, a C 1 -C4 alkylthio group, a C 3 - C cycloalkoxyl group, a carboxyl group, a C 2 -C7 alkoxycarbonyl group, a benzyloxy group; a phenyl group optionally substituted; or two R substituents represent together a C1-C4 alkylenedi- oxy group;
  • n an integer from 0 to 4.
  • halogen examples include fluorine, chlorine, bromine, iodine.
  • C 1 -C6 alkyl examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- butyl, tert-butyl, n-pentyl, 3-methylbutyl, n-hexyl, 3,3-dimethylbutyl.
  • C 3 -C6 cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.
  • Examples of C 4 -C7 cycloalkylalkyl are cyclopropylmethyl, cyclobutylmethyl, cyclopen- tylmethyl, cyclohexylmethyl.
  • C 1 -C6 alkoxyl examples are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy.
  • C1-C6 haloalkoxyl are trifluoromethoxy, 1 , 1 ,2,2-tetrafluoroethoxy, 1 , 1 ,2,3 ,3 ,3 -hexa-fluoro-propoxy.
  • C 1 -C4 alkylthio examples include methylthio, ethylthio, propylthio, isopropylthio.
  • C 2 -C7 alkoxycarbonyl examples include methoxy-carbonyl, ethoxy carbonyl.
  • C 1 -C4 alkylenedioxy examples are methylenedioxy, ethylenedioxy, propylenedioxy.
  • C3-C6 cycloalkoxyl examples include cyclopropoxy, cyclopentoxy, cyclohexyloxy.
  • heterocyclic rings having from 4 to 7 atoms, possibly halogenated are: azet- idine, 3,3-difluoroazetidine, pyrrolidine, piperidine, 4-fluoropiperidine, morpholine.
  • Phenyl optionally substituted refers to a phenyl group which can have one or more sub- stituents, the same or different, preferably selected from the following groups: halogen atoms, Ci-C4 alkyls, Ci-C4 haloalkyls, C1-C4 alkoxyl s, Ci-C4 haloalkoxyls.
  • halogen atoms Ci-C4 alkyls
  • Ci-C4 haloalkyls Ci-C4 alkyls
  • C1-C4 alkoxyl s Ci-C4 haloalkoxyls.
  • An object of the present invention therefore also relates to benzoylphenyl-formamidines that are a) mixtures of unseparated geometrical isomers, mixtures of partially separated geometrical isomers, single geometrical isomers; b) in the form of salts obtained by the addition of inorganic or organic acids; c) in the form of crystalline adducts with urea, in any molar or weight ra- tio, preferably from 1 : 1 to 1 :5; d) in the form of inclusion compounds with substances having a solubility in water lower than 150 g/1 and a melting point higher than 85°C, such as, for example, dimethylsulfone.
  • Examples of compounds having general formula (I) of particular interest for their biological activity are compounds wherein R 1; R 2 , R3, R4, R and n have the meanings indicated in Ta- ble 1
  • salts of compounds having general formula (I) of particular interest for their biological activity are compounds having formula (I) wherein Ri, R2, R3, Rt, R and n have the meanings specified hereunder, salified by addition with the acid specified hereunder, in
  • Preferred compounds having general formula (I) are those wherein Ri represents ethyl, R 2, R 3 and R4 represent methyl, R represents a halogen, a CF 3 group, an OCF 3 group or an OCH 3 group and n has the values 0-2, R being equal or different when n is equal to 2.
  • Ri represents ethyl
  • R 2 , R 3 and R4 represent methyl
  • R represents a CI or Br atom
  • n has the values 0-2, R being equal or different when n is equal to 2, are even more preferred.
  • aniline having formula (II) a) treatment of aniline having formula (II) with an acetal having formula RiR 2 NC(OR5), wherein R5 represents an alkyl, according to what is described in "Synthetic Communications", 24 (1994), pages 1617-1624; b) treatment of aniline having formula (II) with an amide having formula HCONR1R2 in the presence of POCI 3 or SOCI2 , according to what is described in "Tetrahedron", 46 (1990), pages 6058-61 12;
  • the compound having formula (II) can be prepared by acylation of the corresponding aniline, protected as carbamate having formula (IV) with a derivative of benzoic acid (VI), in the presence of a Lewis acid and subsequent deprotection of the compound (III) in the presence of a base, as indicated in reaction scheme 2, according to methods well-known in organic chemistry.
  • the compound having formula (III) can be easily deprotected to give the compound having formula (II) by reaction with a base such as sodium or potassium hydroxide in a mixture of water/alcohol according to what is described in "Protective groups in Organic Synthesis” Theodora W. Green, Third Edition (1999).
  • the compound having formula (IV) can be easily prepared by reaction of the commercial compound having formula (X) with a compound having formula CICOOR 5 , wherein R 5 represents an alkyl group in the presence of a base, preferably potassium carbonate, according to reaction scheme 4.
  • the compound having formula (II) can also be obtained by acylation of p- xylene with a derivative of benzoic acid (VI), for example a benzoyl chloride suitably substituted, in the presence of a Lewis acid, followed by the subsequent nitration of the product having formula (XI), thus obtained, and reduction of the nitro-derivative (XII) to give the corresponding aniline having formula (II), according to reaction scheme 5.
  • a derivative of benzoic acid (VI) for example a benzoyl chloride suitably substituted
  • reaction conditions for the reduction of compound (XII) envisage the use of zinc powder in glacial acetic acid according to what is described in "Comprehensive Organic Transformations", R. Larock (1999), Second Edition.
  • Compound (XI) can also be easily obtained by reaction between p-xylene and a benzo- nitrile suitably substituted, in the presence of palladium catalysts according to what is described in "J. Org. Chem.”, 71 (2006), pages 3551-3558.
  • a further alternative for obtaining the compound having formula (II) is the reaction between the compound having formula (X) and a benzoyl chloride having formula (V), under such conditions as to obtain first the formation of the anilide and then acylation of the same to give compound (XIII) which, by reaction with KF and alumina, leads to the formation of compound (II), according to reaction scheme 6.
  • reaction conditions for obtaining compound (II) from the product having formula (XIII) envisage the use of KF and alumina with the use of microwaves in the absence of a solvent, according to what is described in "Chin.J.Chem ", 29 (201 1), pages 2209-2212.
  • the preferred reaction conditions for obtaining compound (II) from the product having formula (XIV) envisage the use of AICI 3 and irradiation of microwaves in the absence of a solvent, according to what is described in "Indian. J. Chem., Section B: Organic Chemistry Including Medicinal Chemistry", 44 (2005), pages 635-637.
  • the compounds having general formula (I) have an extremely high fungicidal activity which is exerted with respect to numerous phytopathogenic fungi that attack important agricultural crops.
  • a further object of the present invention therefore relates to the use of compounds having formula (I) for the control of phytopathogenic fungi of agricultural crops.
  • phytopathogenic fungi that can be effectively treated and fought with the compounds having general formula (I) are those belonging to the species of Basidiomycetes, As- corn cetes, Deuteromycetes or imperfect fungi, Ooraycetes: Puccinia spp., Ustilago spp., Tilletia spp., Uromyces spp., Phakopsora spp., Rhizoctonia spp., Erysiphe spp., Sphaerotheca spp., Pod- osphaera spp., Uncinula spp., Helminthosporium spp., Rhynchosporium spp., Pyrenophora spp., Monilinia spp., Sclerotinia spp., Septoria spp.
  • Mycosphaerella spp Venturia spp., Botrytis spp., Alternaria spp., Fusarium spp., Cercospora spp., Cercosporella herpotrichoides, Colleto- trichum spp., Pyricularia oryzae, Sderotium spp., Phytophtora spp., Pythium spp., Plasmopara viticola, Peronospora spp., Pseudoperonospora cubensis, Bremia lactucae.
  • the main crops that can be protected with the compounds according to the present inven- tion comprise cereals (wheat, barley, rye, oats, rice, corn, sorghum, etc.), fruit trees (apple-trees, pear-trees, plum-trees, peach-trees, almond-trees, cherry-trees, banana-trees, vines, strawberries, raspberries, blackberries, etc.), citrus fruits (orange-trees, lemon-trees, tangerine-trees, grape- fruit-trees, etc.), legumes (beans, peas, lentils, soybean, etc.), vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, aubergines, peppers, etc.), cucurbits (pump- kin, courgettes, cucumbers, melons, water-melons, etc.), oleoginous plants (sunflower, rape, peanut, castor-oil, coconut,
  • the compounds having formula (I) have proved to be extremely effective in the control of Plasmopara viticola on vines, Phytophtora infestans and Botrytis Cinerea on tomatoes, Puccinia recondita, Erysiphe graminis, Helminthosporium teres, Septoria nodorum and Fusarium spp. on cereals, in the control of Phakopsora pachyrhizi on soya, in the control of Uromyces Appendiculatus on beans, in the control of Venturia inaequalis on apple-trees, in the control of Sphaerotheca f liginea on cucumbers.
  • the compounds having general formula (I) are also effective in the control of phytopathogenic bacteria and viruses, such as, for example, Xanthomonas spp., Pseudomonas spp., Erwinia amylovora, the mosaic virus of tobacco.
  • the compounds having general formula (I) are capable of exerting a fungicidal action of both a curative and preventive nature and have an extremely low or zero phytotoxicity on the crops treated.
  • a further object of the present invention therefore relates to fungicidal compositions comprising one or more compounds having formula (I), a solvent and/or a solid or liquid diluent, possibly one or more surfactants and other agronomically acceptable co-formulants.
  • compositions can be in the form of dry powders, wettable powders, emulsifia- ble concentrates, emulsions, microemulsions, pastes, granules, water-dispersible granules, solutions, suspensions, etc. : the selection of the type of composition depends on the specific use.
  • the fungicidal compositions are prepared in the known way, for example by diluting or dissolving the active substance with a solvent medium and/or a solid or liquid diluents, possibly in the presence of surfactants.
  • silica silica, kaolin, ben- tonite, talc, fossil flour, dolomite, calcium carbonate, magnesia, gypsum, clays, synthetic silicates, attapulgite, seppiolite.
  • Liquid solvents or diluents that can be used are, for example, in addition to water, aromatic organic solvents (xylols or mixtures of alkylbenzenes, chlorobenzene, etc.), paraffins (oil fractions), alcohols (methanol, propanol, butanol, octanol, glycerine, etc.), esters (ethyl acetate, isobutyl acetate, alkyl carbonates, alkyl esters of adipic acid, alkyl esters of glutaric acid, alkyl esters of succinic acid, alkyl esters of lactic acid, etc.), vegetable oils (rape oil, sunflower oil, soybean oil, castor oil, corn oil, peanut oil, and their alkyl esters), ketones (cyclohexanone, acetone, acetophenone, isophorone, ethylamylketone, etc.), amides ( ⁇ , ⁇ -dimethylform
  • Surfactants that can be used are sodium, calcium, potassium salts, salts of triethylamine or triethanolamine of alkylnaphthalenesulfonates, polynaphthalenesulfonates, alkyl sulfonates, aryl sulfonates, alkylarylsulfonates, polycarboxylates, sulfosuccinates, alkylsulfosuccinates, lig- nin sulfonates, alkylsulfates; and again, polyethoxylated fatty alcohols, polyethoxylated al- kylphenols, polyethoxylated esters of sorbitol, polypropoxy polyethoxylates (block polymers), can be used.
  • the fungicidal compositions can also contain special additives for particular purposes, for example, antifreeze agents such as propylene glycol, or adhesion agents such as Arabic rubber, polyvinyl alcohol, polyvinylpyrrolidone, etc.
  • antifreeze agents such as propylene glycol
  • adhesion agents such as Arabic rubber, polyvinyl alcohol, polyvinylpyrrolidone, etc.
  • the concentration of the compounds having general formula (I) in the above compositions can vary within a wide range; they can generally range from 1% to 90% by weight with respect to the total weight of the composition, preferably from 5 to 50% by weight with respect to the total weight of the composition.
  • fungicidal compositions containing the compounds having general formula (I), compatible therewith such as, for example, fungicides different from those having general formula (I), phy- toregulators, antibiotics, herbicides, insecticides, fertilizers and/or mixtures thereof.
  • fungicidal compounds examples include:
  • a further object of the present invention therefore relates to fungicidal compositions comprising at least one compound having general formula (I) and at least one other known fungicide.
  • Fungicidal compositions containing at least one benzoylphenyl-formamidine having formula (I) and one or more known fungicides are those wherein one or more compounds having general formula (I) are combined with one or more known fungicides belonging to the following classes:
  • azoles selected from azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, epoxy-conazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prochloraz, prothiocona- zole, simeconazole, tebu-conazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticon- azole;
  • amines inhibitors of ergosterol biosynthesis selected from aldimorph, dodemorph, fenpropi- morph, fenpropidin, spiroxamine, tridemorph;
  • SDHI succinate-dehydrogenase
  • strobilurins selected from azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrameto-strobin, pyraoxostrobin, trifloxystrobin;
  • aniline-pyramidines selected from pyrimethanil, mepanipyrim, cyprodinil,
  • dicarboxyimides selected from iprodione, procymidone
  • phtalimides selected from tra captafol, captan, folpet;
  • SAR systemic acquired resistance
  • phenylpyrroles selected from fenpiclonil, fludioxonil;
  • acylalanines selected from benalaxyl, benalaxyl-M, furalaxyl, metalaxyl, metal axyl-M;
  • dithiocarbamates selected from maneb, mancozeb, propineb, zineb;
  • rameic compounds selected from Bordeaux mixture, carpropamid, copper hydroxide, copper oxychloride, copper sulfate, copper salycilate; s) other fungicides selected from chlorothalonil, fenhexamid, fenpyrazamine, fluazinam, sylthi- ofam, tebufloquin, zoxamide, dodine, guazatine, iminoctadine.
  • the fungicidal compounds are indicated in the present description with their ISO international name; the chemical structures and their CAS and IU AC names are indicated in Alan Wood's Website (www. alanwood. net). Compendium of Pesticide Common Names; the physic- chemical data and the biological characteristics of most of these compounds are indicated in "Pesticide Manual", C.D.S. Tomlin, 15 a Edition, 2009, British Crop Production Council.
  • compositions containing at least one compound having formula (I) (component
  • A) and at least another known fungicide are those consisting of:
  • Component A i.e. the compounds having general formula (I), of the previous compositions C1-C75 are described and exemplified in the following tables 4 and 6 and are specifically the following compounds having general formula (I) wherein the substituents have the meanings indicated hereunder:
  • the compound 1.1 is the salt of the compound having general formula (I) wherein the various substituents have the meanings indicated hereunder and the acid used for salification is hydrochloric acid:
  • compositions containing a compound having general formula (I) (component A) and a known fungicide (component B), can be evaluated by applying the Colby formula ("Weeds, 1967, 15, pages 20-22):
  • E t is the expected effectiveness percentage for the composition containing compounds A and B at doses d A + de
  • EA is the effectiveness percentage observed for component A at a dose d a
  • E B is the effectiveness percentage observed for component B at a dose ds.
  • E, E A + EBI + E B 2 - (EAXEBI + E A xE B 2 + E B ixE B 2)/100
  • E t is the expected effectiveness percentage for the composition containing compounds A, B l and B2 at doses dA + dei + dB2
  • EA is the effectiveness percentage observed for component A at a dose dA
  • EBI is the effectiveness percentage observed for component B l at a dose dei
  • EB2 is the effectiveness percentage observed for component B2 at a dose de2-
  • the effectiveness observed for the composition A + Bl + B2 (EA+BI+B2) is higher than the expected effectiveness according to the Colby formula ( ⁇ + ⁇ + ⁇ 2 ⁇ ( > 1), there is a synergic effect.
  • the main crops that can be protected with the compositions comprising at least one compound having formula (I), alone or combined with at least one other known active principle comprise cereals (wheat, barley, rye, oats, rice, corn, sorghum, etc.), fruit trees (apple-trees, pear- trees, plum-trees, peach-trees, almond-trees, cherry-trees, banana-trees, vines, strawberries, rasp- berries, blackberries, etc.), citrus fruits (orange-trees, lemon-trees, tangerine-trees, grapefruit- trees, etc.), legumes (beans, peas, lentils, soybean, etc.), vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, aubergines, peppers, etc.), cucurbits (pumpkin, courgettes, cucumbers, melons, water-melons, etc.), oleoginous plants (sunflower, rape, peanut
  • compositions of the present invention have proved to be extremely effective in the control of Plasmopara viticola on vines, Phytophtora infestans and Botrytis Ciner- ea on tomatoes, Puccinia recondita, Erysiphe graminis, Helminthosporium teres, Septoria no- dorum and Fusarium spp. on cereals, in the control of Phakopsora pachyrhizi on soya, in the control of Uromyces Appendiculatiis on beans, in the control of Venturia inaequalis on apple- trees, in the control of Sphaerotheca fuliginea on cucumbers.
  • the compounds having general formula (I) are also effective in the control of phytopathogenic bacteria and viruses, such as, for example, Xanthomonas spp., Pseudomonas spp., Erwinia amylovora, the mosaic virus of tobacco.
  • compositions object of the present invention are capable of exerting a fungicidal ac- tion that can be of a curative, preventive or eradicating nature and generally have an extremely low or zero phytotoxicity on the crops treated.
  • a further object of the present invention therefore relates to the use of compositions comprising at least one benzoylphenyl-formamidine having general formula (I) for the control of phytopathogenic fungi of agricultural crops.
  • compositions comprise a compound having general formula (I) and at least one known active principle
  • weight ratios in the above compositions vary according to the compounds preselected and can normally range from 1 : 100 to 100: 1, preferably from 1 : 10 to 10: 1.
  • the total concentration of active components in the above compositions can vary within a wide range; it generally varies from 1% to 99% by weight with respect to the total weight of the composition, preferably from 5% to 90% by weight with respect to the total weight of the composition.
  • the application of these compositions can be effected on all parts of the plant, for example on the leaves, stems, branches and roots, or on the seeds themselves before being planted, or on the ground in which the plant grows.
  • a further object of the present invention therefore relates to a method for the control of phytopathogenic fungi in agricultural crops, which consists in applying, on any part of the plants to be protected, effective and non-phytotoxic doses of compositions comprising at least one compound having general formula (I) and, optionally, one or more known active principles, compatible therewith.
  • the quantity of compound to be applied for obtaining the desired effect can vary in rela- tion to various factors such as, for example, the compound(s) used, the crop to be preserved, the type of pathogen, the degree of infection, the climatic conditions, the application method, the formulation adopted.
  • reaction mixture was cooled to room temperature, most of the acetone was evaporated, the mixture was diluted with water and extracted with ethyl acetate.
  • a solution of sodium hydroxide obtained by dissolving 28.2 g (0.71 moles) of NaOH in 250 ml of water was trickled, under stirring, onto a solution of 40 g (0.14 moles) of N- methoxycarbonyl-4-benzoyl-2,5-dimethylaniline in 250 ml of ethanol.
  • the reaction mixture was maintained at 90°C for 40 minutes.
  • Catalytic / oluene-sulfonic acid was added to a mixture of 30 g of 4-benzoyl-2,5- dimethylaniline (0.133 moles) and 110 ml of triethyl-orthoformiate (0.67 moles).
  • the organic phase was treated with a solution of NaHCC>3 at 10%, anhydrified on sodium sulfate and evaporated at reduced pressure.
  • the product obtained was washed at room temperature with w-hexane, filtered and dried in air.
  • a sulfonitric mixture obtained by mixing 6.46 ml of nitric acid at 65% and 26 ml of sulfuric acid 95-97%, was added dropwise to this mixture, maintained cold and under vigorous stirring.
  • the raw product obtained was washed at room temperature with «-hexane, filtered and dried in air.
  • the solid product was filtered on a celite bed and the ethanol concentrated at reduced pressure.
  • the raw product thus obtained was washed with a saturated solution of sodium bicarbonate and extracted with ethyl acetate.
  • reaction mixture was further diluted with an additional 4.25 ml of dioxane and after 30' of stirring at room temperature, the precipitate formed was fil- tered.
  • the plants were dry-infected by shaking plants previously infected by Erysiphe graminis over them, in order to spread the inoculum.
  • the plants were then kept in the same cell, in an environment saturated with humidity, at a temperature ranging from 18 to 24°C for 12 days.
  • the phytotoxicity (percentage of leaf necrosis) induced on the wheat seedlings by applying the products was evaluated: in this case the evaluation scale ranges from 0 (completely healthy seedling) to 100 (completely necrotic seedling).
  • Table 7 indicates the results obtained by carrying out the test described on compounds Nr. 1, 1.1, 8, 9, 10, 11 and 21 compared with the following compounds described in WO 00/46184:
  • CR1 N,N-dimethyl-N'-[4-(3-trifluoromethylbenzoyl)-2,5-xylyl-formamidine (compound Nr. 398);
  • CR2 N,N-dimethyl-N'-[4-benzoyl-2,5-xylyl]-formamidine;
  • CR3 N-ethyl-N-methyl-N'-[4-(3-trifluoromethylphenoxy)-2,5-xylyl]formamidine (compound Nr. 45).
  • the plants were kept in an environment saturated with humidity, at a temperature ranging from 18 to 24°C for the incubation period of the fungus (1 day).
  • Table 8 indicates the results obtained by carrying out the test described on compounds nr.
  • CR1 N,N-dimethyl-N'-[4-(3-trifluoromethylbenzoyl)-2,5-xylyl-formamidine (compound Nr. 398);
  • CR2 N,N-dimethyl-N'-[4-benzoyl-2,5-xylyl]-formamidine;
  • CR3 N-ethyl-N-methyl-N'-[4-(3-trifluoromethylphenoxy)-2,5-xylyl]formamidine (compound Nr. 45).
  • the plants were either dry-infected by shaking plants previously infected by different phytopathogens over them in order to spread the inoculum, or infected by spraying a spore suspension of a defined concentration of the inoculum.
  • the plants were then kept in the same cell, in an environment saturated with humidity, at a temperature ranging from 18 to 24°C for 12 days.
  • I, IA + IB - (IAXIB/100)
  • I t is the fungicidal activity of the mixture
  • IA is the fungicidal activity observed for compound A at the dose d A ;
  • IB is the fungicidal activity observed for compound B at the dose de.
  • compositions of the present invention show a strong synergistic effect (synergy factor > 1) with compounds belonging to chemical classes having a very different mechanism of action.
  • Botrytis cinerea Compound 1 / 15 53 - -
  • Rhizoctonia solani Thiophanate-methyl / 250 60 - -

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne de nouvelles benzoylphényl-formamidines de formule générale (I), des compositions fongicides les contenant, et leur utilisation dans la lutte contre les champignons phytopathogènes des cultures agricoles.
PCT/IB2015/051019 2014-02-12 2015-02-11 Benzoylphényl-formamidines ayant une activité fongicide, leurs compositions agronomiques et leur utilisation Ceased WO2015121802A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI2014A000199 2014-02-12
ITMI20140199 2014-02-12

Publications (1)

Publication Number Publication Date
WO2015121802A1 true WO2015121802A1 (fr) 2015-08-20

Family

ID=50336462

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2015/051019 Ceased WO2015121802A1 (fr) 2014-02-12 2015-02-11 Benzoylphényl-formamidines ayant une activité fongicide, leurs compositions agronomiques et leur utilisation

Country Status (3)

Country Link
AR (1) AR099415A1 (fr)
UY (1) UY35992A (fr)
WO (1) WO2015121802A1 (fr)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105510506A (zh) * 2016-01-30 2016-04-20 崔淑华 一种gc-ms/ms测定果蔬中氟唑菌苯胺残留的方法
CN105717223A (zh) * 2016-01-30 2016-06-29 崔淑华 一种gc-ei-ms测定果蔬中氟唑菌苯胺残留的方法
CN106770704A (zh) * 2016-11-21 2017-05-31 河南省农业科学院农业质量标准与检测技术研究所 一种小麦中环氟菌胺残留量的检测方法
WO2017102635A1 (fr) * 2015-12-15 2017-06-22 Syngenta Participations Ag Dérivés de phénylamidine microbiocides
WO2018000526A1 (fr) * 2016-06-26 2018-01-04 江苏辉丰农化股份有限公司 Composition fongicide
WO2018069841A1 (fr) * 2016-10-14 2018-04-19 Pi Industries Ltd Dérivés de phénylamine 4-substitués et leur utilisation pour protéger des cultures par lutte contre des micro-organismes phytopathogènes indésirables
WO2018162999A1 (fr) * 2017-03-07 2018-09-13 Upl Ltd Combinaisons fongicides
WO2018193385A1 (fr) 2017-04-20 2018-10-25 Pi Industries Ltd. Nouveaux composés de phénylamine
WO2018211442A1 (fr) 2017-05-18 2018-11-22 Pi Industries Ltd. Composés de formimidamidine utiles contre des micro-organismes phytopathogènes
WO2019202459A1 (fr) 2018-04-16 2019-10-24 Pi Industries Ltd. Utilisation de composés de phénylamidine substitués en 4 pour lutter contre les maladies dues à la rouille chez les plantes
CN110632226A (zh) * 2019-08-30 2019-12-31 浙江工业大学 基于微波破乳分散液液微萃取和QuEChERS技术测定蔬菜中三唑类农药残留的方法
CN110749672A (zh) * 2019-10-24 2020-02-04 中国热带农业科学院分析测试中心 一种香蕉中啶氧菌酯残留的检测方法
CN112778379A (zh) * 2019-11-07 2021-05-11 华中科技大学 一种在水相溶剂中合成氘代化合物的方法
WO2021094906A1 (fr) 2019-11-12 2021-05-20 Pi Industries Ltd. Nouvelle composition agrochimique comprenant des composés de phénylamidine 4-substitués

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4209319A (en) 1972-12-01 1980-06-24 Ciba-Geigy Corporation Herbicidally active phenylformamidine compounds
WO2000046184A1 (fr) 1999-02-06 2000-08-10 Aventis Cropscience Gmbh Derive n2-phenylamidine
WO2012084812A1 (fr) 2010-12-20 2012-06-28 Isagro Ricerca S.R.L. Amides d'aminoindanes présentant une forte activité fongicide et leurs compositions phytosanitaires
WO2013136275A1 (fr) * 2012-03-15 2013-09-19 Isagro S.P.A. Compositions synergiques à activité fongicide et leur utilisation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4209319A (en) 1972-12-01 1980-06-24 Ciba-Geigy Corporation Herbicidally active phenylformamidine compounds
WO2000046184A1 (fr) 1999-02-06 2000-08-10 Aventis Cropscience Gmbh Derive n2-phenylamidine
WO2012084812A1 (fr) 2010-12-20 2012-06-28 Isagro Ricerca S.R.L. Amides d'aminoindanes présentant une forte activité fongicide et leurs compositions phytosanitaires
WO2013136275A1 (fr) * 2012-03-15 2013-09-19 Isagro S.P.A. Compositions synergiques à activité fongicide et leur utilisation

Non-Patent Citations (25)

* Cited by examiner, † Cited by third party
Title
BULL. CHEM. SOC JPN, vol. 73, 2000, pages 2325 - 2333
CHIN.J.CHEM., vol. 29, 2011, pages 2209 - 2212
GREEN CHEMISTRY, vol. 4, 2002, pages 129 - 133
HELVETICA CHIMICA ACTA, vol. XXIX, 1946, pages 1413 - 1424
HELVETIVA CHIMICA ACTA, vol. 88, 2005, pages 2282 - 2287
INDIAN.J.CHEM., SECTION B: ORGANIC CHEMISTRY INCLUDING MEDICINAL CHEMISTRY, vol. 44, 2005, pages 635 - 637
J. ORG. CHEM., vol. 71, 2006, pages 3551 - 3558
JERRY MARCH: "Advanced Organic Chemistry", 1992, JOHN WILEY & SONS PUB., pages: 1216 - 1217
JOURNAL COMBINATORIAL CHEMISTRY, vol. 11, 2009, pages 126 - 130
JOURNAL OF ORGANIC CHEMISTRY, vol. 26, 1990, pages 2031 - 2031
R. LAROCK: "Comprehensive Organic Transformations", 1999
SYNTHESIS, vol. 10, 2000, pages 1427 - 1430
SYNTHESIS, vol. 13, 2004, pages 2165 - 2168
SYNTHESIS, vol. 13, 2007, pages 1970 - 1978
SYNTHESIS, vol. 13, 2007, pages 1970 - 1980
SYNTHETIC COMMUNICATIONS, vol. 24, 1994, pages 1617 - 1624
TETRAHEDRON LETTERS, vol. 37, 1996, pages 513 - 516
TETRAHEDRON LETTERS, vol. 46, 2005, pages 7627 - 7630
TETRAHEDRON LETTERS, vol. 49, 2008, pages 6715 - 6719
TETRAHEDRON, vol. 46, 1990, pages 6058 - 6112
TETRAHEDRON, vol. 56, 2000, pages 6463 - 6465
TETRAHEDRON, vol. 56, 2000, pages 7199 - 7203
TETRAHEDRON, vol. 56, 2000, pages 8253 - 8262
THEO-DORA W. GREEN: "Protective groups in Organic Synthesis", 1999
WEEDS, vol. 15, 1967, pages 20 - 22

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108366562B (zh) * 2015-12-15 2020-12-22 先正达参股股份有限公司 杀微生物的苯基脒衍生物
US10723695B2 (en) 2015-12-15 2020-07-28 Syngenta Participations Ag Microbiocidal phenylamidine derivatives
WO2017102635A1 (fr) * 2015-12-15 2017-06-22 Syngenta Participations Ag Dérivés de phénylamidine microbiocides
CN108366562A (zh) * 2015-12-15 2018-08-03 先正达参股股份有限公司 杀微生物的苯基脒衍生物
CN105510506A (zh) * 2016-01-30 2016-04-20 崔淑华 一种gc-ms/ms测定果蔬中氟唑菌苯胺残留的方法
CN105717223A (zh) * 2016-01-30 2016-06-29 崔淑华 一种gc-ei-ms测定果蔬中氟唑菌苯胺残留的方法
WO2018000526A1 (fr) * 2016-06-26 2018-01-04 江苏辉丰农化股份有限公司 Composition fongicide
CN109843056A (zh) * 2016-10-14 2019-06-04 印度商皮埃企业有限公司 4-经取代之苯基胺衍生物及其通过对抗不要的植物病原性微生物而保护作物之用途
US11155517B2 (en) 2016-10-14 2021-10-26 Pi Industries Ltd. 4-substituted phenylamine derivatives and their use to protect crops by fighting undesired phytopathogenic micoorganisms
WO2018069841A1 (fr) * 2016-10-14 2018-04-19 Pi Industries Ltd Dérivés de phénylamine 4-substitués et leur utilisation pour protéger des cultures par lutte contre des micro-organismes phytopathogènes indésirables
CN106770704A (zh) * 2016-11-21 2017-05-31 河南省农业科学院农业质量标准与检测技术研究所 一种小麦中环氟菌胺残留量的检测方法
CN106770704B (zh) * 2016-11-21 2019-06-07 河南省农业科学院农业质量标准与检测技术研究所 一种小麦中环氟菌胺残留量的检测方法
US12376592B2 (en) 2017-03-07 2025-08-05 Upl Ltd Fungicidal combinations
US12369585B2 (en) 2017-03-07 2025-07-29 Upl Ltd Fungicidal combinations
WO2018162999A1 (fr) * 2017-03-07 2018-09-13 Upl Ltd Combinaisons fongicides
US11524934B2 (en) 2017-04-20 2022-12-13 Pi Industries Ltd Phenylamine compounds
JP2020517608A (ja) * 2017-04-20 2020-06-18 ピーアイ インダストリーズ リミテッドＰｉ Ｉｎｄｕｓｔｒｉｅｓ Ｌｔｄ 新規フェニルアミン化合物
CN110678442A (zh) * 2017-04-20 2020-01-10 Pi工业有限公司 新型苯胺化合物
AU2018254010B2 (en) * 2017-04-20 2022-05-12 Pi Industries Ltd. Novel phenylamine compounds
WO2018193385A1 (fr) 2017-04-20 2018-10-25 Pi Industries Ltd. Nouveaux composés de phénylamine
WO2018211442A1 (fr) 2017-05-18 2018-11-22 Pi Industries Ltd. Composés de formimidamidine utiles contre des micro-organismes phytopathogènes
WO2019202459A1 (fr) 2018-04-16 2019-10-24 Pi Industries Ltd. Utilisation de composés de phénylamidine substitués en 4 pour lutter contre les maladies dues à la rouille chez les plantes
CN110632226A (zh) * 2019-08-30 2019-12-31 浙江工业大学 基于微波破乳分散液液微萃取和QuEChERS技术测定蔬菜中三唑类农药残留的方法
CN110749672A (zh) * 2019-10-24 2020-02-04 中国热带农业科学院分析测试中心 一种香蕉中啶氧菌酯残留的检测方法
CN112778379A (zh) * 2019-11-07 2021-05-11 华中科技大学 一种在水相溶剂中合成氘代化合物的方法
CN112778379B (zh) * 2019-11-07 2022-10-14 华中科技大学 一种在水相溶剂中合成氘代化合物的方法
WO2021094906A1 (fr) 2019-11-12 2021-05-20 Pi Industries Ltd. Nouvelle composition agrochimique comprenant des composés de phénylamidine 4-substitués

Also Published As

Publication number Publication date
UY35992A (es) 2015-08-31
AR099415A1 (es) 2016-07-20

Similar Documents

Publication Publication Date Title
WO2015121802A1 (fr) Benzoylphényl-formamidines ayant une activité fongicide, leurs compositions agronomiques et leur utilisation
CN103502220B (zh) 具有高杀真菌活性的氨基茚满酰胺及其植物保健组合物
US9040457B2 (en) Phenylamidines having a high fungicidal activity and use thereof
US11477983B2 (en) Synergistic compositions for the protection of agrarian crops and the use thereof
AU2011347585A1 (en) Aminoindanes amides having a high fungicidal activity and their phytosanitary compositions
WO2010109301A1 (fr) Composés benzamidiques à activité fongicide et leur utilisation
WO2013136275A1 (fr) Compositions synergiques à activité fongicide et leur utilisation
US20210100246A1 (en) Pyridyl-formamidines having a fungicidal activity, their agronomic compositions and use thereof
WO2020225700A1 (fr) Composés ayant une activité fongicide, leurs compositions agronomiques et leur utilisation pour lutter contre des champignons phytopathogènes
CA3052519A1 (fr) Derives de triazolethione
BR112019019096B1 (pt) Piridil-formamidinas, composição fungicida, uso de compostos, e, método para controlar os fungos fitopatogênicos em culturas agrícolas
WO2021005512A1 (fr) Composés ayant une activité fongicide, leurs compositions agronomiques et leur utilisation pour lutter contre des champignons phytopathogènes
JP2005511739A (ja) 殺真菌活性を有するチアゾール誘導体
ITMI20120256A1 (it) Fenilammidine ad attivita' fungicida e relativo uso
ITMI20101575A1 (it) Fenilammidine ad elevata attivita' fungicida e relativo uso

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15708338

Country of ref document: EP

Kind code of ref document: A1

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112016016418

Country of ref document: BR

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15708338

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 112016016418

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20160714