WO2012025450A1 - Phenylamidines having a high fungicidal activity and use thereof - Google Patents

Phenylamidines having a high fungicidal activity and use thereof Download PDF

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WO2012025450A1
WO2012025450A1 PCT/EP2011/064210 EP2011064210W WO2012025450A1 WO 2012025450 A1 WO2012025450 A1 WO 2012025450A1 EP 2011064210 W EP2011064210 W EP 2011064210W WO 2012025450 A1 WO2012025450 A1 WO 2012025450A1
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phenyl
spp
hcf
group
atom
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PCT/EP2011/064210
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Marilena Gusmeroli
Lucio Filippini
Franco Pellacini
Paolo Bravini
Alexia Elmini
Matteo Santino Vazzola
Christian Badaracco
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Isagro Ricerca S.R.L.
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Priority to BR112013004220A priority Critical patent/BR112013004220B1/en
Priority to US13/818,622 priority patent/US9040457B2/en
Priority to EP11749396.5A priority patent/EP2608666A1/en
Publication of WO2012025450A1 publication Critical patent/WO2012025450A1/en

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    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/39—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
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    • 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
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    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
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    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/18—Oxygen or sulfur atoms
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    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
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    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

  • the present invention relates to phenylamidines having a high fungicidal activity and their relative use, in particular substituted phenylamidines having a high fungicidal activity and their use for the control of phytopathogenic fungi of important agricultural crops .
  • Phenylamidines having a high fungicidal activity are described in international patent applications WO 2000/46184, WO 2003/093224, WO 2007/031508, WO 2007/031512, WO 2007/031513, WO 2007/031523, WO 2007/031524, WO 2008/110279.
  • An object of the present invention therefore re ⁇ lates to new phenylamidines having general formula (I) :
  • R represents a phenyl, pyridyl, pyrimidyl, pyrazyl or pyridazyl group, all groups substituted by at least a substituent selected from C 1 -C6 polyfluoroalkoxy con ⁇ taining at least one hydrogen atom, C 1 -C6 polyfluoroal- kylthio containing at least one hydrogen atom, C3-C6 cycloalkyl, C3-C6 halocycloalkyl , C3-C6 cycloalkoxy, C 3 - C6 halocycloalkoxy, C -C8 cycloalkylalkoxy, C -C8 halo- cycloalkylalkoxy; said groups phenyl, pyridyl, pyrimidyl, pyrazyl or pyridazyl being optionally sub ⁇ stituted by one or two further substituents , equal to or different from each
  • Ri represents C 2 -C6 alkyl
  • R 2 represents C1-C6 alkyl; or Ri and R2, together with the N atom to which they are bound, form a heterocyclic ring containing from 4 to 7 atoms, optionally substituted by halogen atoms;
  • R3 and R4 equal to or different from each other, represent a hydrogen atom, a halogen atom, a C 1 -C6 al- kyl, a C 1 -C6 alkoxy, a C 1 -C6 haloalkoxy, a CF 3 group, a CF 2 H group, a CFH 2 group, a cyano group.
  • halogen examples include fluorine, chlorine, bro ⁇ mine, 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 1 -C6 haloalkyl examples include fluoromethyl , di- fluoromethyl , trifluoromethyl, chloromethyl , dichloro- methyl, 2, 2, 2-trifluoroethyl, 1 , 1 , 2 , 2-tetrafluoroethyl , pentafluoroethyl , heptafluoropropyl , 4 , 4 , 4-trichloro- butyl, 4, 4-difluoropentyl, 5, 5-difluorohexyl .
  • C 1 -C6 polyfluoroalkoxy group containing at least one hydrogen atom examples include difluoromethoxy, 2,2,2- trifluoroethoxy, 1 , 1 , 2 , 2-tetrafluoroethoxy, 2,2,3,3- tetrafluoropropoxy, 2,2,3,3, 3-pentafluoropropoxy,
  • C1-C6 polyfluoroalkylthio group con ⁇ taining at least one hydrogen atom are difluoromethyl- thio, 2 , 2 , 2-trifluoroethylthio, 1 , 1 , 2 , 2-tetrafluoro- ethylthio, 2, 2, 3, 3-tetrafluoropropylthio, 2 ⁇ 2 ⁇ 3 3 ⁇ 3 pentafluoropropylthio, 1,1,2,3,3, 3-hexafluoropropyl ⁇ thio, 2, 2, 3, 4, 4, 4-hexafluorobutylthio, 4 , 4-difluoro ⁇ pentylthio, 4 , 4 , 5, 5, 5-pentafluoropentylthio, 2,2,3,3,- 4,4,5, 5-octafluoropentylthio, 5, 5-difluorohexylthio .
  • C3-C6 cycloalkyl examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl .
  • Examples of a C3-C6 halocycloalkyl are 2,2- dichlorocyclopropyl , 2, 2-difluorocyclopropyl, 2,2,3,3- tetrafluorocyclobutyl , 3, 3-difluorocyclopentyl, 2- fluorocyclohexyl .
  • C3-C6 cycloalkoxy examples are cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexyloxy .
  • C3-C6 halocycloalkoxy examples are 2,2- dichlorocyclopropoxy, 2 , 2-difluorocyclopropoxy, 2,2,- 3 , 3-tetrafluorocyclobutoxy, 3, 3-difluorocyclopentoxy, 2-fluorocyclohexyloxy .
  • C -C8 cycloalkylalkoxy examples are cyclopropyl- methoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclo- hexylmethoxy, cyclohexylethoxy .
  • C -C8 halocycloalkylalkoxy examples are 2,2- dichlorocyclopropylmethoxy, 2, 2-difluorocyclopropyl- methoxy, 2 , 2 , 3 , 3-tetrafluorocyclobutylmethoxy, 3,3- difluorocyclopentylmethoxy, 4, 4-difluorocyclohexyl- methoxy, 4, 4-difluorocyclohexylethoxy.
  • heterocyclic rings with from 4 to 7 atoms optionally halogenated are: azetidine, 3,3- difluoroazetidine, pyrrolidine, piperidine, 4- fluoropiperidine, morpholine.
  • Preferred compounds of general formula (I) are those wherein:
  • R represents a phenyl, pyridyl, pyrimidyl, pyrazyl or pyridazyl group, all groups substituted by at least a substituent selected from difluoromethoxy, 2,2,2- trifluoroethoxy, 1 , 1 , 2 , 2-tetrafluoroethoxy, 2,2,3,3- tetrafluoropropoxy, 2,2,3,3, 3-pentafluoropropoxy, 2,2,3,4,4, 4-hexafluorobutoxy, 2, 2, 3, 3, 4, 4, 5, 5-octa- fluoropentoxy, cyclopentoxy, cyclohexyloxy, cyclopro ⁇ pylmethoxy or cyclohexylmethoxy; said phenyl, pyridyl, pyrimidyl, pyrazyl or pyridazyl group being optionally substituted by one or two further substituents , equal to or different from each other, selected from a substitu
  • - Ri represents ethyl, n-propyl, isopropyl
  • R 2 represents methyl; or Ri and R 2 , together with the N atom to which they are bound, represent a pyrrolidyl, piperidyl or morpholyl group;
  • - R represents a phenyl group substituted by at least a substituent selected from difluoromethoxy, 2,2,2- trifluoroethoxy, 1 , 1 , 2 , 2-tetrafluoroethoxy, 2,2,3,3- tetrafluoropropoxy, 2,2,3,3, 3-pentafluoropropoxy, 2,2,3,4,4, 4-hexafluorobutoxy, 2, 2, 3, 3, 4, 4, 5, 5-octa- fluoropentoxy, cyclopentoxy, cyclohexyloxy, cyclopro- pylmethoxy or cyclohexylmethoxy; said phenyl group be ⁇ ing optionally substituted by one or two further sub- stituents, equal to or different from each other, se ⁇ lected from a fluorine atom, a chorine atom, methyl or trifluoromethyl ;
  • - Ri represents ethyl, n-propyl, isopropyl
  • R 2 represents a methyl
  • Ri and R 2 together with the N atom to which they are bound, represent a pyrrolidyl, piperidyl or morpholyl- group;
  • the compound having formula (II) can be prepared by reduction of the corresponding nitro-derivative having formula (III), as indicated in reaction scheme 2, ac ⁇ cording to methods well-known in organic chemistry, as described for example in "Advanced Organic Chemistry", Jerry March, 4 a Edition, 1992, John Wiley & Sons Pub., pages 1216-1217 and references cited therein.
  • Scheme 2
  • the compound having formula (III) can be prepared by reaction of the compound having formula (IV) with a compound having formula RX, wherein X is a leaving group such as, for example, a halogen atom, a mesylate or a tosylate group, in the presence of a base, pref ⁇ erably potassium carbonate or sodium hydride, according to reaction scheme 3:
  • the compound having formula (III) can also be obtained by reaction of the compound having formula (V) , wherein Y represents a halogen atom, with a compound having the formula RSH, in the presence of a base, preferably potassium carbonate or sodium hydride, according to reaction scheme 4.
  • a base preferably potassium carbonate or sodium hydride
  • the compounds having formula (IV) are prepared by reacting, in the presence of a palladium catalyst, a compound having formula (V) with potassium thioacetate and subsequently saponifying the thioester thus ob ⁇ tained, according to what is described in "Tetrahedron Letters", 48 (2007), pages 3033-3037.
  • the compounds having general formula (I) contain ⁇ ing polyfluoroalkoxy, (halo ) cycloalkoxy or (halo)- cycloalkylalkoxy groups on the ring R, can also be ob- tained, by means of known techniques, starting from hy ⁇ droxy- [ (hetero) arylthio] phenylformamidines (obtainable as described in examples 4, 5 and 6) by addition to fluorinated olefins, as described in more detail in ex- ample 7, or by etherification with the corresponding halides or tosylates.
  • the compounds having general formula (I) have an extremely high fungicidal activity which is exerted with respect to numerous phytopatho- genie fungi which attack important agricultural crops.
  • phytopathogenic fungi which can be ef ⁇ fectively treated and fought with the compounds having general formula (I) are those belonging to the groups of Basidiomycetes , Ascomycetes, Deuteromycetes or im- perfect fungi, Oomycetes: Puccinia spp .
  • Ustilago spp. Tilletia spp., Uromyces spp., Phakopsora spp., Rhizoc- tonia spp., Erysiphe spp., Sphaerotheca spp., Podos- phaera 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 herpotrichoid.es, Colletotrichum spp., Pyricularia oryzae, Sclerotium spp., Phytophtora spp., Pythium spp., Plasmopara viti- cola, Peronospora spp., Pseudoperonospora cubensis, Bremia lactucae .
  • the main crops which can be protected with the com ⁇ pounds according to the present invention comprise ce ⁇ reals (corn, barley, rye, oats, rice, maize, sorghum, etc.), fruit trees (apples, pears, plums, peaches, al ⁇ monds, cherries, bananas, vines, strawberries, raspber ⁇ ries, blackberries, etc.), citrus trees (oranges, lem ⁇ ons, mandarin oranges, grapefruits, etc.), leguminous plants (beans, peas, lentils, soybean, etc.), horticul- tural plants (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, aubergines, pep ⁇ pers, etc.), cucurbitaceae (pumpkins, courgettes, cu ⁇ cumbers, melons, water-melons, etc.), oleaginous plants (sunflower, rape, peanut, castor oil plant, coconut, etc.), tobacco, coffee, tea
  • the compounds having formula (I) have proved to be extremely effective in the control of Phytophtora infestans and Botrytis Cinerea on tomatoes; Puccinia recondita r Erisiphae graminis , Helminthospo- rium teres, Septoria nodorum and Fusarium spp . on cere ⁇ als, in the control of Phakopsora pachyrhizi on soy ⁇ bean, in the control of Uromyces Appendiculatus on beans, in the control of Venturia inaequalis on apple trees, in the control of Sphaerotheca fuliginea on cu- cumbers .
  • the compounds having formula (I) are also effective in the control of bacteria and phytopa- thogenic viruses, such as for example Xanthomonas spp . , Pseudomonas spp., Erwinia amylovora, tobacco mosaic vi ⁇ rus .
  • the compounds having formula (I) are capable of ex ⁇ erting a fungicidal action of both a curative and pre ⁇ ventive nature and have an extremely low or zero phyto- toxicity on the crops treated.
  • a further object of the present invention therefore relates to the use of the compounds having formula (I) for the control of phytopathogenic fungi of agricul ⁇ tural crops .
  • fungicidal compositions containing the compounds of the present invention suitably formulated.
  • a further object of the present invention relates to fungicidal compositions comprising one or more com- pounds having formula (I), a solvent and/or solid or liquid diluent, optionally a surface-active agent.
  • the above fungicidal compositions can be in the form of dry powders, wettable powders, emulsifying con ⁇ centrates, emulsions, microemulsions , pastes, granu- lates, water dispersible granules, solutions, suspen- sions, etc.: the choice of the type of composition will depend 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 diluent, optionally in the presence of sur ⁇ factants .
  • Solid diluents or supports which can be used for example are: silica, kaolin, bentonite, talc, infu- sorial earth, dolomite, calcium carbonate, magnesia, gypsum, clays, synthetic silicates, attapulgite, sepio- lite .
  • Liquid solvents or diluents which can be used are for example, in addition to water, aromatic organic solvents (xylols or blends of alkylbenzols , chloroben- zene, etc.), paraffins (petroleum 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 (cyclohexa- none, acetone, acetophenone, isophorone, ethylamylke- tone, etc.), amides
  • the fungicidal compositions can also contain spe ⁇ cial additives for particular purposes, such as for ex- ample, antifreeze agents such as propylene glycol, or adhesive agents, such as Arabic rubber, polyvinyl alco ⁇ hol, polyvinyl pyrrolidone, etc..
  • spe ⁇ cial additives for particular purposes, such as for ex- ample, antifreeze agents such as propylene glycol, or adhesive agents, such as Arabic rubber, polyvinyl alco ⁇ hol, polyvinyl pyrrolidone, etc.
  • fungicidal compositions containing the compounds of general formula (I) can be added to the fungicidal compositions containing the compounds of general formula (I), such as, for ex ⁇ ample, fungicides different from those having general formula (I), phytoregulators , antibiotics, herbicides, insecticides, fertilizers and/or mixtures thereof.
  • fungicides different from those having general formula (I) which can be included in the fungi- cidal compositions of the present invention are: aci- benzolar, ametoctradin, amisulbrom, ampropylfos, anilazine, azaconazole, azoxystrobin, benalaxyl, benal- axyl-M, benomyl, benthiavalicarb, bitertanol, bixafen, blasticidin-S , boscalid, bromuconazole, bupirimate, buthiobate, captafol, captan, carbendazim, carboxin, carpropamid, chinomethionat , chloroneb, chlorothalonil , chlozolinate, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, debacar
  • the concentration of phenylamidine compounds having general formula (I) in the above compositions can vary within a wide range; it generally ranges from 1% to 90% by weight with respect to the total weight of the com ⁇ position, preferably from 5% to 50% by weight with re ⁇ spect to the total weight of the composition.
  • compositions can be ef ⁇ fected on all parts of the plant, for example on the leaves, stems, branches and roots, or on the seeds themselves before sowing, 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 the ap ⁇ plication of effective dosages of the compounds of for ⁇ mula (I), used as such or formulated in fungicidal com ⁇ positions as described above.
  • the quantity of compound to be applied for obtain- ing the desired effect can vary in relation to differ- ent factors, such as, for example, the compound used, the crop to be preserved, the type of pathogen, the de ⁇ gree of infection, the climatic conditions, the appli ⁇ cation method, the formulation adopted.
  • Doses of compound ranging from 10 g to 5 kg per hectare of agricultural crop generally provide a suffi ⁇ cient control.
  • reaction mixture is cooled to room temperature, filtered on a celite bed, diluted with water and extracted with ethyl acetate.
  • the or ⁇ ganic phase is anhydrified with sodium sulfate, and then filtered and evaporated.
  • Catalytic p-toluenesulfonic acid is added to a mix ⁇ ture of 25 g of 4- (3-difluoromethoxyphenylthio) -2, 5- xylidine (0.085 moles) and 141 ml of triethyl- orthoformiate (0.85 moles) .
  • the temperature is brought to reflux and the mixture is kept under stirring for 3 hours.
  • the reaction trend is controlled with TLC (elu- ent hexane/ethyl acetate 8:2) .
  • the mixture is concentrated at reduced pres ⁇ sure and the raw product obtained dissolved in methyl- ene chloride (234 ml); 14.3 ml of N-ethylmethylamine (0.17 moles) are added dropwise.
  • the mixture is kept under stirring for 3 hours at 40°C and, after TLC control (eluent hexane/ethyl acetate 8:2), is concentrated at reduced pressure. 20 g of the desired product are obtained.
  • Catalytic p-toluenesulfonic acid is added to a mixture of 15 g (0.06 moles) of product obtained as de- scribed in Example 5 and 100 ml of triethylorthofor- miate (0.6 moles) .
  • the temperature is brought to reflux and the mixture kept under stirring for 3 hours.
  • the reaction trend is controlled with TLC (eluent hex- ane/ethyl acetate 8:2) .
  • the reaction mixture is concentrated at reduced pres ⁇ sure and the raw product obtained dissolved in 165 ml of methylene chloride; 10 ml of N-ethylmethylamine are added dropwise. The mixture is kept under stirring for 3 hours at 40°C.
  • the reaction is diluted with water and extracted with ethyl acetate; the organic phase is anhydrified with sodium sulfate and concentrated to give 5.7 g of residue.
  • the crude product thus obtained is purified by means of a silica gel chromatographic column eluting with hexane/ethyl acetate/triethylamine 97:2:1.
  • Leaves of wheat plants of the Salgemma variety grown in pots in a conditioned environment kept at 20°C and 70% of relative humidity (R.H.), were treated by spraying on both sides of the leaves with the compounds under examination, dispersed in hydroacetonic solu ⁇ tions at 20% by volume of acetone.
  • the plants were infected under dry conditions by shaking over them, in order to distribute the inoculum, plants previously infected by Erysiphe graminis .
  • the plants were then maintained in the same cell, in a humidity-saturated environment and at a tempera ⁇ ture ranging from 18 to 24°C for 12 days. At the end of this period, the external symptoms of the pathogen appeared and it was therefore possible to proceed with the evaluation of the intensity of the in ⁇ fection, on both the parts treated directly with the products (T) , and also on the parts which had developed during the test (NT) , by means of a visible percentage evaluation scale of the area of affected leafs; the scale comprises, as extremes, the value 100 (healthy plant) and the value 0 (completely infected plant) .
  • the phytotoxicity was evaluated (percentage of leaf necrosis) induced on the wheat plants by the application of the products: in this case, the evaluation scale varies from 0 (completely healthy plant) to 100 (completely necrotized plant) .
  • Table 4 shows the results obtained by effecting the test described with compounds N. 1, 2, 15, 19 and 23, compared with the following reference products de- scribed in Table 1 of WO 00/46184:
  • Leaves of wheat plants of the Salgemma variety grown in pots in a conditioned environment kept at 20°C and 70% of relative humidity (R.H.), were treated by spraying on both sides of the leaves with the compounds under examination, dispersed in hydroacetonic solutions at 20% by volume of acetone.
  • R.H. relative humidity
  • the plants After being sprayed, the plants were kept in a hu ⁇ midity-saturated environment at a temperature ranging from 18 to 24°C for the incubation period of the fungus (1 day) .
  • the external symptoms of the pathogen appeared and it was therefore possible to proceed with the evaluation of the intensity of the in- fection, on both the parts treated directly with the products (T) , and also on the parts which had developed during the test (NT) , by means of a visible percentage evaluation scale of the area of affected leafs; the scale comprises, as extremes, the value 100 (healthy plant) and the value 0 (completely infected plant) .
  • the phytotoxicity was evaluated (percentage of leaf necrosis) induced on the wheat plants by the application of the products: in this case, the evaluation scale varies from 0 (completely healthy plant) to 100 (completely necrotized plant) .
  • Table 5 shows the results obtained by effecting the test described with compounds N. 1, 2, 15, 19 and 23, compared with the following reference products de ⁇ scribed in Table 1 of WO 00/46184:
  • the compounds N. 1, 2, 15, 19 and 23 proved to be less phytotoxic and/or more active with respect to the reference products.

Abstract

New phenylamidines are described, having general formula (I) and their use for the control of phytopathogenic fungi.

Description

PHENYLAMIDINES HAVING A HIGH FUNGICIDAL ACTIVITY AND USE THEREOF
The present invention relates to phenylamidines having a high fungicidal activity and their relative use, in particular substituted phenylamidines having a high fungicidal activity and their use for the control of phytopathogenic fungi of important agricultural crops .
Phenylamidines having a high fungicidal activity are described in international patent applications WO 2000/46184, WO 2003/093224, WO 2007/031508, WO 2007/031512, WO 2007/031513, WO 2007/031523, WO 2007/031524, WO 2008/110279.
The products described in these documents, however, are often unsatisfactory from the point of view of both the level of activity with respect to phytopathogenic fungi and also, or alternatively, from the point of view of phytotoxicity with respect to important agri¬ cultural crops.
In particular, for example, the compounds N-ethyl-
N-methyl-N' - [4- ( 3-trifluoromethylphenoxy) -2, 5-xilyl] - formamidine, N, N-dimethyl-N' - [ 4- ( 3-trifluoromethylphenoxy) -2, 5-xilyl] formamidine, N, N-dimethyl-N' - [4- ( 3- trifluoromethoxyphenoxy) -2, 5-xilyl] formamidine, N,N- dimethyl-N' - [4- ( 3-trifluoroethoxyphenoxy) -2, 5-xilyl] - formamidine, described in international patent applica¬ tion WO 00/46184, at the doses which allow a good fungicidal activity to be obtained, show a marked leaf ne¬ crosis on cereals, cucumbers, tomatoes and other impor- tant crops: this effect makes their use as fungicides practically unacceptable. On the other hand, the com¬ pound N, N-dimethyl-N' - [ 4- ( 3-trifluoromethylphenylthio ) - 2 , 5-xilyl ] formamidine, also described in international patent application WO 00/46184, proves to be insuffi- cient from the point of view of fungicidal activity, which is only exerted satisfactorily in excessively high dosages.
International patent application WO 2008/110278 de¬ scribes a whole series of (hetero ) aryloxy- and (het- ero)arylthio N, N-dialkyl-N' -phenyl-formamidines with a herbicidal activity, variously substituted on the (het¬ ero) aryloxy and (hetero ) arylthio rings.
The Applicant has now surprisingly found that new phenylamidines characterized by a (hetero ) arylthio group in position 4 of the phenyl, and by particular combinations of substituents on the (hetero ) arylthio ring and on the nitrogen atom, not only exert an excellent fungicidal activity at low doses, but are also well tolerated by many vegetable species, thus allowing the practical use of these compounds for the control of phytopathogenic microorganisms of important agricul¬ tural crops .
An object of the present invention therefore re¬ lates to new phenylamidines having general formula (I) :
Figure imgf000004_0001
wherein
R represents a phenyl, pyridyl, pyrimidyl, pyrazyl or pyridazyl group, all groups substituted by at least a substituent selected from C1-C6 polyfluoroalkoxy con¬ taining at least one hydrogen atom, C1-C6 polyfluoroal- kylthio containing at least one hydrogen atom, C3-C6 cycloalkyl, C3-C6 halocycloalkyl , C3-C6 cycloalkoxy, C3- C6 halocycloalkoxy, C -C8 cycloalkylalkoxy, C -C8 halo- cycloalkylalkoxy; said groups phenyl, pyridyl, pyrimidyl, pyrazyl or pyridazyl being optionally sub¬ stituted by one or two further substituents , equal to or different from each other, selected from halogen atom, C1-C6 alkyl, C1-C6 haloalkyl;
Ri represents C2-C6 alkyl;
R2 represents C1-C6 alkyl; or Ri and R2, together with the N atom to which they are bound, form a heterocyclic ring containing from 4 to 7 atoms, optionally substituted by halogen atoms;
R3 and R4, equal to or different from each other, represent a hydrogen atom, a halogen atom, a C1-C6 al- kyl, a C1-C6 alkoxy, a C1-C6 haloalkoxy, a CF3 group, a CF2H group, a CFH2 group, a cyano group.
Examples of halogen are fluorine, chlorine, bro¬ mine, iodine.
Examples of C1-C6 alkyl are methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, n-pentyl, 3-methylbutyl , n-hexyl, 3,3- dimethylbutyl .
Examples of C1-C6 haloalkyl are fluoromethyl , di- fluoromethyl , trifluoromethyl, chloromethyl , dichloro- methyl, 2, 2, 2-trifluoroethyl, 1 , 1 , 2 , 2-tetrafluoroethyl , pentafluoroethyl , heptafluoropropyl , 4 , 4 , 4-trichloro- butyl, 4, 4-difluoropentyl, 5, 5-difluorohexyl .
Examples of C1-C6 polyfluoroalkoxy group containing at least one hydrogen atom are difluoromethoxy, 2,2,2- trifluoroethoxy, 1 , 1 , 2 , 2-tetrafluoroethoxy, 2,2,3,3- tetrafluoropropoxy, 2,2,3,3, 3-pentafluoropropoxy,
1,1,2,3,3, 3-hexafluoropropoxy, 2,2,3,4,4, 4-hexafluoro- butoxy, 4 , 4-difluoropentoxy, 4 , 4 , 5, 5, 5-pentafluoro- pentoxy, 2, 2, 3, 3, 4, 4, 5, 5-octafluoropentoxy, 5,5- difluorohexyloxy .
Examples of C1-C6 polyfluoroalkylthio group con¬ taining at least one hydrogen atom are difluoromethyl- thio, 2 , 2 , 2-trifluoroethylthio, 1 , 1 , 2 , 2-tetrafluoro- ethylthio, 2, 2, 3, 3-tetrafluoropropylthio, 2^2^ 3 3 ^ 3 pentafluoropropylthio, 1,1,2,3,3, 3-hexafluoropropyl¬ thio, 2, 2, 3, 4, 4, 4-hexafluorobutylthio, 4 , 4-difluoro¬ pentylthio, 4 , 4 , 5, 5, 5-pentafluoropentylthio, 2,2,3,3,- 4,4,5, 5-octafluoropentylthio, 5, 5-difluorohexylthio .
Examples of C3-C6 cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl .
Examples of a C3-C6 halocycloalkyl are 2,2- dichlorocyclopropyl , 2, 2-difluorocyclopropyl, 2,2,3,3- tetrafluorocyclobutyl , 3, 3-difluorocyclopentyl, 2- fluorocyclohexyl .
Examples of C3-C6 cycloalkoxy are cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexyloxy .
Examples of C3-C6 halocycloalkoxy are 2,2- dichlorocyclopropoxy, 2 , 2-difluorocyclopropoxy, 2,2,- 3 , 3-tetrafluorocyclobutoxy, 3, 3-difluorocyclopentoxy, 2-fluorocyclohexyloxy .
Examples of C -C8 cycloalkylalkoxy are cyclopropyl- methoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclo- hexylmethoxy, cyclohexylethoxy .
Examples of C -C8 halocycloalkylalkoxy are 2,2- dichlorocyclopropylmethoxy, 2, 2-difluorocyclopropyl- methoxy, 2 , 2 , 3 , 3-tetrafluorocyclobutylmethoxy, 3,3- difluorocyclopentylmethoxy, 4, 4-difluorocyclohexyl- methoxy, 4, 4-difluorocyclohexylethoxy.
Examples of heterocyclic rings with from 4 to 7 atoms optionally halogenated are: azetidine, 3,3- difluoroazetidine, pyrrolidine, piperidine, 4- fluoropiperidine, morpholine.
Representative examples of compounds having gener- al formula (I) are those wherein R, Ri, R2, R3 and R have the meanings indicated in Table 1.
Figure imgf000007_0001
Table 1
Figure imgf000007_0002
-HCF2CF20-phenyl -CH2CH2OCH2CH2- Me Me-HCF2CF20-phenyl Et Me H Me-HCF2CF20-phenyl Et Me Me CF3-HCF2CF20-phenyl Et Me Me CF2H-HCF2CF20-phenyl Et Me H CF3-HCF2CF20-phenyl Et Me CF2H Me-HCF2CF20-phenyl Et Me CI CI-HCF2CF20-phenyl Et Me Me CI-HCF2CF20-phenyl Et Me Me H-HCF2CF20-phenyl Et Me H Me-HCF2CF20-phenyl Et Me Me CN-HCF2CF20-phenyl Et Me Me OMe-HCF2CF2S-phenyl Et Me Me Me-HCF2CF20-phenyl Et Me Me Me-HCF2CF20-phenyl - (CH2) 4- Me Me-HCF2CF20-phenyl - (CH2) 5- Me Me-HCF2CF20-phenyl -CH2CH2OCH2CH2- Me Me-HCF2CF2S-phenyl Et Me Me Me
3-HCF20-phenyl Et Me Me Me
3-HCF20-phenyl - (CH2) 4- Me Me
3-HCF20-phenyl - (CH2) 5- Me Me
3-HCF20-phenyl -CH2CH2OCH2CH2- Me Me
3-HCF2S-phenyl Et Me Me Me
4-HCF20-phenyl Et Me Me Me
4-HCF20-phenyl - (CH2) 4- Me Me
4-HCF20-phenyl - (CH2) 5- Me Me 4-HCF20-phenyl -CH2CH2OCH2CH2- Me Me
4-HCF2S-phenyl Et Me Me Me
3-CF3CH20-phenyl Et Me Me Me
3-CF3CH20-phenyl - (CH2) 4- Me Me
3-CF3CH20-phenyl - (CH2) 5- Me Me
3-CF3CH20-phenyl -CH2CH2OCH2CH2- Me Me
3-CF3CH2S-phenyl Et Me Me Me
4-CF3CH20-phenyl Et Me Me Me
4-CF3CH20-phenyl - (CH2) 5- Me Me-HCF2CF2CH20-phenyl Et Me Me Me-HCF2CF2CH20-phenyl - (CH2) 4- Me Me-HCF2CF2CH20-phenyl - (CH2) 5- Me Me-HCF2CF2CH20-phenyl -CH2CH2OCH2CH2- Me Me-HCF2CF2CH20-phenyl Et Me Me Me-HCF2CF2CH2S-phenyl Et Me Me Me-HCF2CF2CH20-phenyl - (CH2) 4- Me Me-HCF2CF2CH20-phenyl - (CH2) 5- Me Me-HCF2CF2CH20-phenyl -CH2CH2OCH2CH2- Me Me-CF3CF2CH20-phenyl Et Me Me Me-CF3CF2CH20-phenyl - (CH2) 4- Me Me-CF3CF2CH20-phenyl - (CH2) 5- Me Me-CF3CF2CH20-phenyl Et Me Me Me-CF3CF2CH20-phenyl - (CH2) 4- Me Me-CF3CF2CH20-phenyl - (CH2) 5- Me Me-CF3CHFCF20-phenyl Et Me Me Me-CF3CHFCF20-phenyl Et Me Me Me 3-CF3CHFCF2CH20-phenyl Et Me Me Me
4-CF3CHFCF2CH20-phenyl Et Me Me Me-HCF2CF2CF2CF2CH20-phenyl Et Me Me Me-HCF2CF2CF2CF2CH20-phenyl Et Me Me Me
4-F-3-HCF20-phenyl Et Me Me Me
4-F-3-HCF20-phenyl - (CH2) 5- Me Me
4-Cl-3-HCF20-phenyl Et Me Me Me
4-Cl-3-HCF20-phenyl - (CH2) 5- Me Me
4-Me-3-HCF20-phenyl Et Me Me Me
2, 4-F2-3-HCF20-phenyl Et Me Me Me
4, 5-F2-3-HCF20-phenyl Et Me Me Me
2-F-3-HCF20-phenyl Et Me Me Me
5-F-3-HCF20-phenyl Et Me Me Me
3-F-4-HCF20-phenyl Et Me Me Me
3-F-4-HCF20-phenyl - (CH2) 5- Me Me
3-Cl-4-HCF20-phenyl Et Me Me Me
3-Cl-4-HCF20-phenyl - (CH2) 5- Me Me
3-Me-4-HCF20-phenyl Et Me Me Me
3-CF3-4-HCF20-phenyl Et Me Me Me
2-F-4-HCF20-phenyl Et Me Me Me
2-Cl-4-HCF20-phenyl Et Me Me Me
3, 5-F2-4-HCF20-phenyl Et Me Me Me
4-F-3-HCF2CF20-phenyl Et Me Me Me
4-F-3-HCF2CF20-phenyl - (CH2) 5- Me Me
4-Cl-3-HCF2CF20-phenyl Et Me Me Me
4-Cl-3-HCF2CF20-phenyl - (CH2) 5- Me Me -Me-3-HCF2CF20-phenyl Et Me Me Me, 4-F2-3-HCF2CF20-phenyl Et Me Me Me, 5-F2-3-HCF2CF20-phenyl Et Me Me Me
2-F-3-HCF2CF20-phenyl Et Me Me Me
5-F-3-HCF2CF20-phenyl Et Me Me Me
3-F-4-HCF2CF20-phenyl Et Me Me Me
3-F-4-HCF2CF20-phenyl - (CH2) 5- Me Me -Cl-4-HCF2CF20-phenyl Et Me Me Me -Cl-4-HCF2CF20-phenyl - (CH2) 5- Me Me -Me-4-HCF2CF20-phenyl Et Me Me Me-CF3-4-HCF2CF20-phenyl Et Me Me Me
2-F-4-HCF2CF20-phenyl Et Me Me Me -Cl-4-HCF2CF20-phenyl Et Me Me Me, 5-F2-4-HCF2CF20-phenyl Et Me Me Me
4-F-3-CF3CH20-phenyl Et Me Me Me
4-F-3-CF3CH20-phenyl - (CH2) 5- Me Me
4-Cl-3-CF3CH20-phenyl Et Me Me Me
4-Cl-3-CF3CH20-phenyl - (CH2) 5- Me Me
4-Me-3-CF3CH20-phenyl Et Me Me Me, 4-F2-3-CF3CH20-phenyl Et Me Me Me, 5-F2-3-CF3CH20-phenyl Et Me Me Me
2-F-3-CF3CH20-phenyl Et Me Me Me
5-F-3-CF3CH20-phenyl Et Me Me Me
3-F-4-CF3CH20-phenyl Et Me Me Me
3-F-4-CF3CH20-phenyl - (CH2) 5- Me Me
3-Cl-4-CF3CH20-phenyl Et Me Me Me 3-Cl-4-CF3CH20-phenyl - (CH2) 5- Me Me
3-Me-4-CF3CH20-phenyl Et Me Me Me
2-F-4-CF3CH20-phenyl Et Me Me Me
2-Cl-4-CF3CH20-phenyl Et Me Me Me
3, 5-F2-4-CF3CH20-phenyl Et Me Me Me
4-F-3-HCF2CF2CH20-phenyl Et Me Me Me
4-F-3-HCF2CF2CH20-phenyl - (CH2) 5- Me Me-Cl-3-HCF2CF2CH20-phenyl Et Me Me Me-Cl-3-HCF2CF2CH20-phenyl - (CH2) 5- Me Me-Me-3-HCF2CF2CH20-phenyl Et Me Me Me
2, 4-F2-3-HCF2CF2CH20- Et Me Me Me phenyl
4, 5-F2-3-HCF2CF2CH20- Et Me Me Me phenyl
2-F-3-HCF2CF2CH20-phenyl Et Me Me Me
5-F-3-HCF2CF2CH20-phenyl Et Me Me Me
3-F-4-HCF2CF2CH20-phenyl Et Me Me Me
3-F-4-HCF2CF2CH20-phenyl - (CH2) 5- Me Me-Cl-4-HCF2CF2CH20-phenyl Et Me Me Me-Cl-4-HCF2CF2CH20-phenyl - (CH2) 5- Me Me-Me-4-HCF2CF2CH20-phenyl Et Me Me Me
2-F-4-HCF2CF2CH20-phenyl Et Me Me Me-Cl-4-HCF2CF2CH20-phenyl Et Me Me Me
3, 5-F2-4-HCF2CF2CH20- Et Me Me Me phenyl
5-HCF2CF20-2-pyridyl Et Me Me Me
5-HCF20-2-pyridyl Et Me Me Me 5-CF3CH20-2-pyridyl Et Me Me Me
5-HCF2CF2CH20-2-pyridyl Et Me Me Me
2-HCF2CF20-4-pyridyl Et Me Me Me
2-HCF20-4-pyridyl Et Me Me Me
2-CF3CH20-4-pyridyl Et Me Me Me
2-HCF2CF2CH20-4-pyridyl Et Me Me Me
2-HCF2CF20-5-pyridyl Et Me Me Me
2-HCF20-5-pyridyl Et Me Me Me
2-CF3CH20-5-pyridyl Et Me Me Me
2-HCF2CF20-5-pyrimidyl Et Me Me Me
2-HCF20-5-pyrimidyl Et Me Me Me
2-CF3CH20-5-pyrimidyl Et Me Me Me
5-HCF2CF20-2-pyrazyl Et Me Me Me
5-HCF20-2-pyrazyl Et Me Me Me
5-CF3CH20-2-pyrazyl Et Me Me Me
6-HCF2CF20-3-pyridazyl Et Me Me Me
6-HCF20-3-pyridazyl Et Me Me Me
6-CF3CH20-3-pyridazyl Et Me Me Me
3-cyclohexyl-phenyl Et Me Me Me
4-cyclohexyl-phenyl Et Me Me Me
3-cyclopentyl-phenyl Et Me Me Me
4-cyclopentyl-phenyl Et Me Me Me
3-cyclopropyl-phenyl Et Me Me Me
4-cyclopropyl-phenyl Et Me Me Me
3-cyclopropyl-phenyl - (CH2) 5- Me Me- ( 2 , 2-Cl2-cyclopropyl ) - Et Me Me Me phenyl - ( 2 , 2-F2-cyclopropyl ) - Et Me Me Me phenyl
- ( cyclopentoxy) -phenyl Et Me Me Me- (cyclopentoxy) -phenyl Et Me Me Me- (cyclopentoxy) -phenyl - (CH2) 5- Me Me- (cyclopentoxy) -phenyl - (CH2) 5- Me Me- ( cyclohexyloxy) -phenyl Et Me Me Me- (cyclohexyloxy) -phenyl Et Me Me Me- (cyclopropylmethoxy) - Et Me Me Me phenyl
- (cyclopropylmethoxy) - Et Me Me Me phenyl
- (cyclopropylmethoxy) - - (CH2) 5- Me Me phenyl
- (cyclopropylmethoxy) - - (CH2) 5- Me Me phenyl
- ( 2 , 2-Cl2-cyclopropylEt Me Me Me methoxy) -phenyl
4-2 , 2-Cl2-cyclopropylEt Me Me Me methoxy) -phenyl
3- ( 2 , 2-F2-cyclopropyl¬ Et Me Me Me methoxy) -phenyl
-- ( 2 , 2-F2-cyclopropylEt Me Me Me methoxy) -phenyl
3-cyclohexylmethoxy- Et Me Me Me phenyl
-cyclopentoxy-2-pyridyl Et Me Me Me- (cyclopropylmethoxy) - Et Me Me Me 2-pyridyl 2-cyclopentoxy-5- Et Me Me Me
pyrimidyl
2- ( cyclopropylmethoxy) - Et Me Me Me
5-pyrimidyl
5-cyclopentoxy-2-pyrazyl Et Me Me Me
5- (cyclopropylmethoxy) - Et Me Me Me
2-pyrazyl
6-cyclopentoxy-3- Et Me Me Me
pyridazyl
6- (cyclopropylmethoxy) - Et Me Me Me
3-pyridazyl
Preferred compounds of general formula (I) are those wherein:
- R represents a phenyl, pyridyl, pyrimidyl, pyrazyl or pyridazyl group, all groups substituted by at least a substituent selected from difluoromethoxy, 2,2,2- trifluoroethoxy, 1 , 1 , 2 , 2-tetrafluoroethoxy, 2,2,3,3- tetrafluoropropoxy, 2,2,3,3, 3-pentafluoropropoxy, 2,2,3,4,4, 4-hexafluorobutoxy, 2, 2, 3, 3, 4, 4, 5, 5-octa- fluoropentoxy, cyclopentoxy, cyclohexyloxy, cyclopro¬ pylmethoxy or cyclohexylmethoxy; said phenyl, pyridyl, pyrimidyl, pyrazyl or pyridazyl group being optionally substituted by one or two further substituents , equal to or different from each other, selected from a fluo¬ rine atom, a chlorine atom, methyl or trifluoromethyl ;
- Ri represents ethyl, n-propyl, isopropyl;
- R2 represents methyl; or Ri and R2, together with the N atom to which they are bound, represent a pyrrolidyl, piperidyl or morpholyl group;
- R3 and R represent methyl.
More preferred compounds of general formula (I) are those wherein:
- R represents a phenyl group substituted by at least a substituent selected from difluoromethoxy, 2,2,2- trifluoroethoxy, 1 , 1 , 2 , 2-tetrafluoroethoxy, 2,2,3,3- tetrafluoropropoxy, 2,2,3,3, 3-pentafluoropropoxy, 2,2,3,4,4, 4-hexafluorobutoxy, 2, 2, 3, 3, 4, 4, 5, 5-octa- fluoropentoxy, cyclopentoxy, cyclohexyloxy, cyclopro- pylmethoxy or cyclohexylmethoxy; said phenyl group be¬ ing optionally substituted by one or two further sub- stituents, equal to or different from each other, se¬ lected from a fluorine atom, a chorine atom, methyl or trifluoromethyl ;
- Ri represents ethyl, n-propyl, isopropyl;
- R2 represents a methyl;
or Ri and R2, together with the N atom to which they are bound, represent a pyrrolidyl, piperidyl or morpholyl- group;
- R3 and R represent methyl.
The compounds having general formula (I) are pre- pared from the corresponding aniline having formula (II), according to the following reaction scheme 1:
Scheme 1
Figure imgf000017_0001
(ID (I)
Various methods for effecting this transformation are known in literature; the most widely used methods are the following:
a) treatment of aniline having formula (II) with an acetal having the formula R1R2NC (OR5) , wherein R5 repre¬ sents 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 the formula HCONR1R2 in the presence of POCI3 or SOCI2, according to what is described in "Tet¬ rahedron", 46 (1990), pages 6058-6112;
c) treatment of aniline having formula (II) with an ortho-ester having the formula HC(ORs), wherein R5 represents an alkyl, to form the corresponding imino- ether followed by heating of the same in the presence of an amine having the formula HNR1R2, according to what is described in US 4,209,319;
d) treatment of aniline having formula (II) with phosgene to form the corresponding isocyanate followed by reaction with an amide having the formula HCONR1R2 , according to what is described in WO 00/46184;
e) treatment of aniline having formula (II) with C2H50CH=NCN to form an N-cyanoamidine followed by reac¬ tion with an amine having the formula HNR1R2 , according to what is described in WO 00/46184;
f) treatment of aniline having formula (II) with
N, N-dimethylformamide in the presence of a sulfonyl- chloride, such as for example, 2-pyridylsulfonyl- chloride or phenylsulfonylchloride, to form the corre¬ sponding dimethylamidine ( Ri=R2=Me) followed by reaction with an amine having the formula HNR1R2 , according to what is described in "Tetrahedron", 56 (2000), pages 8253-8262 and in "Journal Combinatorial Chemistry", 11 (2009) , pages 126-130.
The compound having formula (II) can be prepared by reduction of the corresponding nitro-derivative having formula (III), as indicated in reaction scheme 2, ac¬ cording to methods well-known in organic chemistry, as described for example in "Advanced Organic Chemistry", Jerry March, 4a Edition, 1992, John Wiley & Sons Pub., pages 1216-1217 and references cited therein. Scheme 2
Figure imgf000019_0001
(III) (ID
The preferred reaction conditions for these sub¬ strates envisage the use of tin chloride in concen- trated hydrochloric acid, according to what is de¬ scribed in detail in international patent application WO 00/46184.
The compound having formula (III) can be prepared by reaction of the compound having formula (IV) with a compound having formula RX, wherein X is a leaving group such as, for example, a halogen atom, a mesylate or a tosylate group, in the presence of a base, pref¬ erably potassium carbonate or sodium hydride, according to reaction scheme 3:
Scheme 3
Figure imgf000019_0002
(IV) (III) Alternatively, the compound having formula (III) can also be obtained by reaction of the compound having formula (V) , wherein Y represents a halogen atom, with a compound having the formula RSH, in the presence of a base, preferably potassium carbonate or sodium hydride, according to reaction scheme 4.
Scheme 4
Figure imgf000020_0001
(V) (III)
The compounds having formula (IV) are prepared by reacting, in the presence of a palladium catalyst, a compound having formula (V) with potassium thioacetate and subsequently saponifying the thioester thus ob¬ tained, according to what is described in "Tetrahedron Letters", 48 (2007), pages 3033-3037.
The compounds having general formula (I) contain¬ ing polyfluoroalkoxy, (halo ) cycloalkoxy or (halo)- cycloalkylalkoxy groups on the ring R, can also be ob- tained, by means of known techniques, starting from hy¬ droxy- [ (hetero) arylthio] phenylformamidines (obtainable as described in examples 4, 5 and 6) by addition to fluorinated olefins, as described in more detail in ex- ample 7, or by etherification with the corresponding halides or tosylates.
As already mentioned, the compounds having general formula (I) have an extremely high fungicidal activity which is exerted with respect to numerous phytopatho- genie fungi which attack important agricultural crops.
Examples of phytopathogenic fungi which can be ef¬ fectively treated and fought with the compounds having general formula (I) are those belonging to the groups of Basidiomycetes , Ascomycetes, Deuteromycetes or im- perfect fungi, Oomycetes: Puccinia spp . , Ustilago spp., Tilletia spp., Uromyces spp., Phakopsora spp., Rhizoc- tonia spp., Erysiphe spp., Sphaerotheca spp., Podos- phaera 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 herpotrichoid.es, Colletotrichum spp., Pyricularia oryzae, Sclerotium spp., Phytophtora spp., Pythium spp., Plasmopara viti- cola, Peronospora spp., Pseudoperonospora cubensis, Bremia lactucae .
The main crops which can be protected with the com¬ pounds according to the present invention comprise ce¬ reals (corn, barley, rye, oats, rice, maize, sorghum, etc.), fruit trees (apples, pears, plums, peaches, al¬ monds, cherries, bananas, vines, strawberries, raspber¬ ries, blackberries, etc.), citrus trees (oranges, lem¬ ons, mandarin oranges, grapefruits, etc.), leguminous plants (beans, peas, lentils, soybean, etc.), horticul- tural plants (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, aubergines, pep¬ pers, etc.), cucurbitaceae (pumpkins, courgettes, cu¬ cumbers, melons, water-melons, etc.), oleaginous plants (sunflower, rape, peanut, castor oil plant, coconut, etc.), tobacco, coffee, tea, cacao, sugar beet, sugar cane, cotton.
In particular, the compounds having formula (I) have proved to be extremely effective in the control of Phytophtora infestans and Botrytis Cinerea on tomatoes; Puccinia recondita r Erisiphae graminis , Helminthospo- rium teres, Septoria nodorum and Fusarium spp . on cere¬ als, in the control of Phakopsora pachyrhizi on soy¬ bean, in the control of Uromyces Appendiculatus on beans, in the control of Venturia inaequalis on apple trees, in the control of Sphaerotheca fuliginea on cu- cumbers .
Furthermore, the compounds having formula (I) are also effective in the control of bacteria and phytopa- thogenic viruses, such as for example Xanthomonas spp . , Pseudomonas spp., Erwinia amylovora, tobacco mosaic vi¬ rus .
The compounds having formula (I) are capable of ex¬ erting a fungicidal action of both a curative and pre¬ ventive nature and have an extremely low or zero phyto- toxicity on the crops treated.
A further object of the present invention therefore relates to the use of the compounds having formula (I) for the control of phytopathogenic fungi of agricul¬ tural crops .
For practical uses in agriculture, it is often pre¬ ferable to use fungicidal compositions containing the compounds of the present invention suitably formulated.
A further object of the present invention relates to fungicidal compositions comprising one or more com- pounds having formula (I), a solvent and/or solid or liquid diluent, optionally a surface-active agent.
The above fungicidal compositions can be in the form of dry powders, wettable powders, emulsifying con¬ centrates, emulsions, microemulsions , pastes, granu- lates, water dispersible granules, solutions, suspen- sions, etc.: the choice of the type of composition will depend 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 diluent, optionally in the presence of sur¬ factants .
Solid diluents or supports which can be used for example are: silica, kaolin, bentonite, talc, infu- sorial earth, dolomite, calcium carbonate, magnesia, gypsum, clays, synthetic silicates, attapulgite, sepio- lite .
Liquid solvents or diluents which can be used, are for example, in addition to water, aromatic organic solvents (xylols or blends of alkylbenzols , chloroben- zene, etc.), paraffins (petroleum 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 (cyclohexa- none, acetone, acetophenone, isophorone, ethylamylke- tone, etc.), amides (N, N-dimethylformamide, N-methyl- pyrrolidone, etc.), sulfoxides and sulfones (dimethyl- sulfoxide, dimethyl sulfone, etc.), and mixtures thereof .
Sodium salts, calcium salts, potassium salts, salts of triethylamine or triethanolamine of alkylnaphthale- nesulfonates, polynaphthalenesulfonates, alkyl sul¬ fonates, aryl sulfonates, alkylaryl sulfonates, poly- carboxylates , sulfosuccinates, alkyl sulfosuccinates, ligninsulfonates, alkyl sulfates, can be used as sur- factants; as also polyethoxylated fatty alcohols, poly- ethoxylated alkylphenols , polyethoxylated esters of sorbitol, polypropoxy polyethoxylates (block polymers) .
The fungicidal compositions can also contain spe¬ cial additives for particular purposes, such as for ex- ample, antifreeze agents such as propylene glycol, or adhesive agents, such as Arabic rubber, polyvinyl alco¬ hol, polyvinyl pyrrolidone, etc..
When desired, other compatible active principles can be added to the fungicidal compositions containing the compounds of general formula (I), such as, for ex¬ ample, fungicides different from those having general formula (I), phytoregulators , antibiotics, herbicides, insecticides, fertilizers and/or mixtures thereof.
Examples of fungicides different from those having general formula (I) which can be included in the fungi- cidal compositions of the present invention are: aci- benzolar, ametoctradin, amisulbrom, ampropylfos, anilazine, azaconazole, azoxystrobin, benalaxyl, benal- axyl-M, benomyl, benthiavalicarb, bitertanol, bixafen, blasticidin-S , boscalid, bromuconazole, bupirimate, buthiobate, captafol, captan, carbendazim, carboxin, carpropamid, chinomethionat , chloroneb, chlorothalonil , chlozolinate, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, debacarb, dichlofluanid, di- chlone, diclobutrazol , diclomezine, dicloran, diclocy- met, diethofencarb, difenoconazole, diflumetorim, dime- thirimol, dimethomorph, dimoxystrobin, diniconazole, dinocap, dipyrithione, ditalimfos, dithianon, dode- morph, dodine, edifenphos, epoxiconazole, etaconazole, ethaboxam, ethirimol, ethoxyquin, etridiazole, fa- moxadone, fenamidone, fenaminosulf, fenapanil, fenari- mol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin, ferbam, ferimzone, fluazinam, fludioxonil, flu- metover, flumorph, fluopicolide, fluopyram, fluoroim- ide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flu- triafol, fluxapyroxad, folpet, fosetyl-aluminium, fube- ridazole, furalaxyl, furametpyr, furconazole, furcona- zole-cis, guazatine, hexaconazole, hymexazol, hydroxy- quinoline sulfate, imazalil, imibenconazole, iminoc- tadine, ipconazole, iprobenfos, iprodione, iso- prothiolane, iprovalicarb, isopyrazam, isotianil, kasu- gamycin, kresoxim-methyl, mancopper, mancozeb, mandipropamid, maneb, mebenil, mepanipyrim, mepronil, meptyldinocap, metalaxyl, metalaxyl-M, metconazole, methfuroxam, metiram, metominostrobin, metrafenone, metsulfovax, myclobutanil , natamycin, nicobifen, ni- trothal-isopropyl , nuarimol, ofurace, orysastrobin, oxadixyl, oxpoconazole, oxycarboxin, pefurazoate, pen- conazole, pencycuron, penflufen, pentachlorofenol e suoi sali, penthiopyrad, phthalide, picoxystrobin, piperalin, Bordeaux mixture, polyoxins, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, proquinazid, prothiocarb, prothioconazole, pyracarbolid, pyraclostrobin, pyrametostrobin, pyraox- ystrobin, pyrazophos, pyribencarb, pyrifenox, pyrimethanil , pyriofenone, pyroquilon, pyroxyfur, qui- nacetol, quinazamid, quinconazole, quinoxyfen, quintoz- ene, rabenzazole, copper hydroxide, copper oxychloride, copper (I) oxide, copper sulfate, sedaxane, silthiofam, simeconazole, spiroxamine, streptomycin, tebuconazole, tebufloquin, tetra-conazole, thiabendazole, thiadi- fluor, thicyofen, thifluzamide, thiophanate, thiophan- ate-methyl, thiram, tiadinil, tioxymid, tolclofos- methyl, tolylfluanid, triadimefon, triadimenol, triari- mol, triazbutil, triazoxide, tricyclazole, tridemorf, trifloxystrobin, triflumizole, triforine, triticona- zole, uniconazole, uniconazole-P, validamycin, valifenalate, vinclozolin, zineb, ziram, sulfur, zox- amide .
The concentration of phenylamidine compounds having general formula (I) in the above compositions can vary within a wide range; it generally ranges from 1% to 90% by weight with respect to the total weight of the com¬ position, preferably from 5% to 50% by weight with re¬ spect to the total weight of the composition.
The application of these compositions can be ef¬ fected on all parts of the plant, for example on the leaves, stems, branches and roots, or on the seeds themselves before sowing, 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 the ap¬ plication of effective dosages of the compounds of for¬ mula (I), used as such or formulated in fungicidal com¬ positions as described above.
The quantity of compound to be applied for obtain- ing the desired effect can vary in relation to differ- ent factors, such as, for example, the compound used, the crop to be preserved, the type of pathogen, the de¬ gree of infection, the climatic conditions, the appli¬ cation method, the formulation adopted.
Doses of compound ranging from 10 g to 5 kg per hectare of agricultural crop generally provide a suffi¬ cient control.
The following examples are provided for a better understanding of the invention for illustrative and non-limiting purposes of the same.
EXAMPLE 1
Preparation of 2-nitro-5- (3-difluoromethoxyphenylthio) - p-xylene [nitroderivative of formula (III) ]
4.36 g (0.109 moles) of sodium hydride are sus¬ pended in 80 ml of N, N-dimethylformamide at 0°C. 20 g of 4-nitro-2 , 5-dimethylthiophenol (0.109 moles) dis¬ solved in 67 ml of N, N-dimethylformamide are added dropwise under stirring. 24.4 g of l-bromo-3- (difluoromethoxy) benzene (0.109 moles) dissolved in 20 ml of N, N-dimethylformamide are then added dropwise; catalytic Cu° and CuCl are subsequently added and the reaction temperature is brought to 150 °C for 1 h.
After GC control, the reaction mixture is cooled to room temperature, filtered on a celite bed, diluted with water and extracted with ethyl acetate. The or¬ ganic phase is anhydrified with sodium sulfate, and then filtered and evaporated.
The product thus obtained is purified on silica gel eluting with hexane/ethyl acetate 9:1. 30 g of the desired product are obtained. GC-MS : M+ = 325
EXAMPLE 2
Preparation of 4- (3-di luoromethoxyphenylthio) -2 , 5- xylidine [aniline of formula (II) ]
7.7 ml of glacial acetic acid (0.135 moles) are added to a solution of 30 g of 2-nitro-5- ( 3-difluoro¬ methoxyphenylthio ) -p-xylene (0.092 moles) in ¾0 (40 ml) and ethanol (400 ml); 34.7 g of Fe in powder form (0.621 moles) are carefully added to the reaction mix¬ ture kept under stirring at 60°C. The temperature is brought to 90°C and the mixture is kept under stirring for 1.5 hours. When the reaction is completed (GC and TLC analyses), the mixture is cooled to room tempera- ture; the solid is filtered on a celite bed. The etha¬ nol is concentrated at reduced pressure. The crude product obtained is washed with a saturated solution of sodium bicarbonate and extracted with ethyl acetate.
The organic phase is washed with ¾0, anhydrified on sodium sulfate, filtered and evaporated to give 25 g of the desired product. GC-MS : M+ = 295 ESEMPIO 3
Preparation of N-ethyl-N-methyl-N' - [4- (3-difluoro- methoxyphenylthio) -2 , 5-xylyl ] formamidine [Compound .1 ]
Catalytic p-toluenesulfonic acid is added to a mix¬ ture of 25 g of 4- (3-difluoromethoxyphenylthio) -2, 5- xylidine (0.085 moles) and 141 ml of triethyl- orthoformiate (0.85 moles) . The temperature is brought to reflux and the mixture is kept under stirring for 3 hours. The reaction trend is controlled with TLC (elu- ent hexane/ethyl acetate 8:2) . When the reaction is completed, the mixture is concentrated at reduced pres¬ sure and the raw product obtained dissolved in methyl- ene chloride (234 ml); 14.3 ml of N-ethylmethylamine (0.17 moles) are added dropwise. The mixture is kept under stirring for 3 hours at 40°C and, after TLC control (eluent hexane/ethyl acetate 8:2), is concentrated at reduced pressure. 20 g of the desired product are obtained.
GC-MS: M+ = 364. 1H-NMR (CDC13) δ = 1.19 (t, 3H) ; 2.20 (s, 3H) ; 2.28 (s,3H); 2.97 (s, 3H) ; 3.35 (bq, 2H) ; 6.65 (t, 1H) ; 6.70 (bs, 1H) ; 6.80 (bs, 1H) ; 6.85-7.35 (c, 4H) ; 7.50 (bs, 1H) EXAMPLE 4
Preparation of 2-nitro-5- (3-hydroxyphenylthio) -p-xylene [nitroderivative of formula (IV) ]
A mixture of 18.9 g of 3-mercaptophenol (0.150 moles), 32.9 g of 2-nitro-5-bromo-p-xylene (0.143 moles) and K2C03 (0.143 moles) in 95 ml of N,N- dimethylformamide is stirred at room temperature for 2 hours. A solution of HC1 at 10% is added under stirring; the mixture is diluted with ¾0 and extracted with ethyl acetate. The organic phase is washed again with water, anhydrified on sodium sulfate, filtered and evaporated. 20 g of solid product are obtained, which is used as such for the subsequent reaction.
GC-MS: M+ = 275
EXAMPLE 5
Preparation of 4- (3-hydroxyphenylthio) -2 , 5-xylidine
6.3 ml of glacial acetic acid (0.11 moles) are added to a solution of 20 g of the product obtained in Example 4 (0.076 moles) in 328 ml of ethanol and 33 ml of ¾0; 29.7 g of Fe in powder form (0.53 moles) are carefully added to the reaction mixture kept under stirring at 60°C. The temperature is brought to 90°C and the mixture is kept under stirring for 1.5 hours.
When the reaction is complete (GC and TLC analy- ses), the mixture is cooled to room temperature; the solid is filtered on a celite bed. The ethanol is con¬ centrated at reduced pressure. The product obtained is washed with a saturated solution of sodium bicarbonate and extracted with ethyl acetate. The organic phase is washed with ¾0, anhydrified on sodium sulfate, filtered and evaporated to give 15 g of the desired product.
GC-MS: M+ = 245 EXAMPLE 6
Preparation of N-ethyl-N-methyl-N' - [4- (3-hydroxyphenyl- thio) -2 , 5-xylyl ] formamidine .
Catalytic p-toluenesulfonic acid is added to a mixture of 15 g (0.06 moles) of product obtained as de- scribed in Example 5 and 100 ml of triethylorthofor- miate (0.6 moles) . The temperature is brought to reflux and the mixture kept under stirring for 3 hours. The reaction trend is controlled with TLC (eluent hex- ane/ethyl acetate 8:2) . When the reaction is complete, the reaction mixture is concentrated at reduced pres¬ sure and the raw product obtained dissolved in 165 ml of methylene chloride; 10 ml of N-ethylmethylamine are added dropwise. The mixture is kept under stirring for 3 hours at 40°C. After TLC control (eluent hexane/ethyl acetate 8:2), the reaction mixture is concentrated at reduced pressure. 18 g of the desired product are ob¬ tained, used as such in example 7. GC-MS : M+ = 314
EXAMPLE 7
Preparation of N-ethyl-N-methyl-N' -{4- [3- (1 , 1 ,2 ,2- tetra luoroethoxy) phenylthio] -2 , 5-xylyl } formamidine
[Compound . 2 ]
4.7 g of N-ethyl-N-methyl-N' -[ 4- ( 3-hydroxyphenyl- thio ) -2 , 5-xylyl ] formamidine (0.015 moles), obtained as described in Example 6, and 1.0 g of KOH (0.015 moles) are suspended in 43 ml of anhydrous toluene and 198 ml of dimethylsulfoxide . The mixture is cooled to -25 °C; a vacuum is created in the apparatus and tetrafluoro- ethylene is fed. After an hour, the reaction mixture is brought back to room temperature and controlled by means of TLC (hexane/ethyl acetate 7:3) .
The reaction is diluted with water and extracted with ethyl acetate; the organic phase is anhydrified with sodium sulfate and concentrated to give 5.7 g of residue. The crude product thus obtained is purified by means of a silica gel chromatographic column eluting with hexane/ethyl acetate/triethylamine 97:2:1.
GC-MS: M+ = 414. 1H-NMR (CDC13) δ = 1.19 (t, 3H) ; 2.20 (s, 3H) ; 2.28 (s,3H); 2.98 (s, 3H) ; 3.37 (bq, 2H) ; 5.85 (tt, 1H) ; 6.72 (bs, 1H) ; 6.82 (bs, 1H) ; 6.85-7.35 (c, 4H) ; 7.50 (bs, 1H)
EXAMPLE 8
Preparation of compounds N. 3-107
Operating analogously to what is described in the previous examples, the compounds having formula (I) re¬ ported in Table 2 were obtained.
Figure imgf000035_0001
Table 2
Figure imgf000035_0002
3-HCF20-phenyl -CH2CH2OCH2CH2- Me Me
4-HCF20-phenyl - (CH2) 5- Me Me
3-CF3CH20-phenyl Et Me Me Me
3-CF3CH20-phenyl - (CH2) 5- Me Me
4-CF3CH20-phenyl Et Me Me Me
4-CF3CH20-phenyl - (CH2) 5- Me Me
3-HCF2CF2CH20-phenyl Et Me Me Me
3-HCF2CF2CH20-phenyl - (CH2) 5- Me Me
4-HCF2CF2CH20-phenyl Et Me Me Me
4-HCF2CF2CH20-phenyl - (CH2) 5- Me Me
3-CF3CF2CH20-phenyl Et Me Me Me
3-CF3CF2CH20-phenyl - (CH2) 5- Me Me
4-CF3CF2CH20-phenyl Et Me Me Me
4-CF3CF2CH20-phenyl - (CH2) 5- Me Me
4-Cl-3-HCF2CF20-phenyl Et Me Me Me
4-Me-3-HCF2CF20-phenyl Et Me Me Me
3-Cl-4-HCF2CF20-phenyl Et Me Me Me
3-Me-4-HCF2CF20-phenyl Et Me Me Me
3-CF3-4-HCF2CF20-phenyl Et Me Me Me
4-Cl-3-HCF2CF20-phenyl - (CH2) 5- Me Me
4-Me-3-HCF2CF20-phenyl - (CH2) 5- Me Me
3-Cl-4-HCF2CF20-phenyl - (CH2) 5- Me Me
3-Me-4-HCF2CF20-phenyl - (CH2) 5- Me Me
3-CF3-4-HCF2CF20-phenyl - (CH2) 5- Me Me
4-F-3-HCF2CF20-phenyl Et Me Me Me
3-F-4-HCF2CF20-phenyl Et Me Me Me 4-F-3-HCF2CF20-phenyl - (CH2) 5- Me Me
3-F-4-HCF2CF20-phenyl - (CH2) 5- Me Me
4-Cl-3-HCF20-phenyl Et Me Me Me
3-Cl-4-HCF20-phenyl Et Me Me Me
4-Cl-3-HCF20-phenyl - (CH2) 5- Me Me
3-Cl-4-HCF20-phenyl - (CH2) 5- Me Me
4-F-3-HCF20-phenyl Et Me Me Me
3-F-4-HCF20-phenyl Et Me Me Me
4-F-3-HCF20-phenyl - (CH2) 5- Me Me
3-F-4-HCF20-phenyl - (CH2) 5- Me Me
4-Cl-3-CF3CH20-phenyl Et Me Me Me
3-Cl-4-CF3CH20-phenyl Et Me Me Me
4-Cl-3-CF3CH20-phenyl - (CH2) 5- Me Me
3-Cl-4-CF3CH20-phenyl - (CH2) 5- Me Me
4-F-3-CF3CH20-phenyl Et Me Me Me
3-F-4-CF3CH20-phenyl Et Me Me Me
4-F-3-CF3CH20-phenyl - (CH2) 5- Me Me
3-F-4-CF3CH20-phenyl - (CH2) 5- Me Me
4-Cl-3-HCF2CF2CH20- Et Me Me Me phenyl
3-Cl-4-HCF2CF2CH20- Et Me Me Me phenyl
4-Cl-3-HCF2CF2CH20- - (CH2) 5- Me Me phenyl
3-Cl-4-HCF2CF2CH20- - (CH2) 5- Me Me phenyl
4-F-3-HCF2CF2CH20-phenyl Et Me Me Me 3-F-4-HCF2CF2CH20-phenyl Et Me Me Me
4-F-3-HCF2CF2CH20-phenyl - (CH2) 5- Me Me
3-F-4-HCF2CF2CH20-phenyl - (CH2) 5- Me Me
3-CF3CFHCF2CH20-phenyl Et Me Me Me
3-HCF2CF2CF2CF2CH20- Et Me Me Me phenyl
4-HCF2CF2CF2CF2CH20- Et Me Me Me phenyl
5-HCF2CF20-2-pyridyl Et Me Me Me
5-HCF20-2-pyridyl Et Me Me Me
5-CF3CH20-2-pyridyl Et Me Me Me
5-HCF2CF2CH20-2-pyridyl Et Me Me Me
5-HCF2CF20-2-pyridyl - (CH2) 5- Me Me
5-HCF20-2-pyridyl - (CH2) 5- Me Me
5-CF3CH20-2-pyridyl - (CH2) 5- Me Me
5-HCF2CF2CH20-2-pyridyl - (CH2) 5- Me Me
2-HCF2CF20-5-pyrimidyl Et Me Me Me
2-HCF20-5-pyrimidyl Et Me Me Me
5-HCF2CF20-2-pyrazyl Et Me Me Me
5-HCF20-2-pyrazyl Et Me Me Me
5-CF3CH20-2-pyrazyl Et Me Me Me
6-HCF2CF20-3-pyridazyl Et Me Me Me
6-HCF20-3-pyridazyl Et Me Me Me
6-CF3CH20-3-pyridazyl Et Me Me Me
3-cyclohexyloxy-phenyl Et Me Me Me
3-cyclohexyloxy-phenyl - (CH2) 5- Me Me
3-cyclopentoxy-phenyl Et Me Me Me 87 3-cyclopentoxy-phenyl - (CH2) 5- Me Me
88 4-cyclohexyloxy-phenyl Et Me Me Me
89 4-cyclohexyloxy-phenyl - (CH2) 5- Me Me
90 4- cyclopentoxy-phenyl Et Me Me Me
91 4- cyclopentoxy-phenyl - (CH2) 5- Me Me
92 3-cyclopropylmethoxy- Et Me Me Me phenyl
93 3-cyclopropylmethoxy- - (CH2) 5- Me Me phenyl
94 4-cyclopropylmethoxy- Et Me Me Me phenyl
95 4-cyclopropylmethoxy- - (CH2) 5- Me Me phenyl
96 4-C1-3- ( cyclopropyl- Et Me Me Me methoxy) -phenyl
97 4-F-3- ( cyclopropyl- Et Me Me Me methoxy) -phenyl
98 3-cyclohexylmethoxy- Et Me Me Me phenyl
99 5-cyclopentoxy-2- Et Me Me Me pyridyl
100 5-cyclopropylmethoxy-2- Et Me Me Me pyridyl
101 2-cyclopropylmethoxy-5- Et Me Me Me pyrimidyl
102 3-HCF2CF20-phenyl Et Me Me H
103 3-HCF2CF20-phenyl Et Me H Me
104 3-HCF2CF20-phenyl Et Me Me CI
105 3-HCF2CF20-phenyl Et Me CI CI 106 3-HCF2CF20-phenyl Et Me Me MeO
107 3-HCF2CF2S-phenyl Et Me Me Me
The compounds were obtained as dense oils. The GC- S (M ) and H-NMR (CDC13) data for the most representa¬ tive compounds are reported in Table 3.
Table 3
Figure imgf000040_0001
1.19 (t,3H); 2.20 (s,3H); 2.28 (s,3H); 2.98 (s,3H); 3.37 (bq,2H); 5.85 (tt,lH); 6.72 (bs,lH); 6.82
448
(bs,lH); 7.0-7.35 (c, 3H); 7.50 (bs,lH)
1.19 (t,3H); 2.20 (s,3H); 2.28 (s,3H); 2.50 (s,3H); 2.98 (s,3H); 3.37 (bq,2H); 5.85 (tt,lH); 6.72 (bs,
428
1H) ; 6.82 (bs,lH); 6.95-7.35 (c, 3H); 7.50 (bs,lH)
1.19 (t,3H); 2.20 (s,3H); 2.28 (s,3H); 2.98 (s,3H); 3.37 (bq,2H); 5.85 (tt,lH); 6.72 (bs,lH); 6.82
482
(bs,lH); 6.90-7.40 (c, 3H); 7.50 (bs,lH)
1.35-1.80 (c, 6H); 2.20 (s,3H); 2.28 (s,3H); 3.30- 3.50 (m,4H); 6.65 (t,lH); 6.70 (bs,lH); 6.80 (bs,
474
1H) ; 6.95-7.35 (c, 3H); 7.50 (bs,lH)
1.19 (t,3H); 2.20 (s,3H); 2.28 (s,3H); 2.98 (s,3H); 3.37 (bq,2H); 5.85 (tt,lH); 6.72 (bs,lH); 6.82
432
(bs,lH); 7.0-7.35 (c,3H); 7.50 (bs,lH)
1.19 (t,3H); 2.20 (s,3H); 2.28 (s,3H); 2.98 (s,3H); 3.37 (bq,2H); 5.85 (tt,lH); 6.72 (bs,lH); 6.82
432
(bs,lH); 7.0-7.35 (c,3H); 7.50 (bs,lH)
1.35-1.80 (c,6H); 2.20 (s,3H); 2.28 (s,3H); 3.30- 3.50 (m,4H); 5.85 (tt,lH); 6.72 (bs, 1H) ; 6.82
458
(bs,lH); 7.0-7.35 (c,3H); 7.50 (bs,lH)
1.35-1.80 (c,6H); 2.20 (s,3H); 2.28 (s,3H); 3.30- 3.50 (m,4H); 5.85 (tt,lH); 6.72 (bs, 1H) ; 6.82
458
(bs,lH); 7.0-7.35 (c,3H); 7.50 (bs,lH)
1.19 (t,3H); 2.20 (s,3H); 2.28 (s,3H); 2.98 (s,3H); 3.37 (bq,2H); 6.65 (tt,lH); 6.72 (bs,lH); 6.82
398
(bs,lH); 7.0-7.35 (c,3H); 7.50 (bs,lH)
1.19 (t,3H); 2.20 (s,3H); 2.28 (s,3H); 2.98 (s,3H); 3.37 (bq,2H); 6.65 (tt,lH); 6.72 (bs,lH); 6.82
398
(bs,lH); 7.0-7.35 (c,3H); 7.50 (bs,lH)
1.35-1.80 (c,6H); 2.20 (s,3H); 2.28 (s,3H); 3.30- 3.50 (m,4H); 6.65 (t,lH); 6.70 (bs,lH); 6.80 (bs,
424
1H) ; 6.95-7.35 (c,3H); 7.50 (bs,lH)
1.19 (t,3H); 2.20 (s,3H); 2.28 (s,3H); 2.98 (s,3H); 3.37 (bq,2H); 6.65 (t,lH); 6.72 (bs,lH); 6.82 (bs,
382
1H) ; 7.0-7.35 (c,3H); 7.50 (bs,lH)
1.35-1.80 (c,6H); 2.20 (s,3H); 2.28 (s,3H); 3.30- 3.50 (m,4H); 6.60 (tt,lH); 6.72 (bs, 1H) ; 6.82
408
(bs,lH); 7.0-7.35 (c,3H); 7.50 (bs,lH)
1.19 (t,3H); 2.20 (s,3H); 2.28 (s,3H); 2.97 (s,3H); 3.35 (bq,2H); 4.25 (q,2H); 6.72 (bs, 1H) ; 6.82
430
(bs,lH); 6.85-7.35 (c,3H); 7.50 (bs,lH)
1.19 (t,3H); 2.20 (s,3H); 2.28 (s,3H); 2.97 (s,3H); 3.35 (bq,2H); 4.25 (q,2H); 6.72 (bs, 1H) ; 6.82
414
(bs,lH); 6.90-7.40 (c,3H); 7.50 (bs,lH)
1.19 (t,3H); 2.20 (s,3H); 2.28 (s,3H); 2.97 (s,3H); 3.35 (bq,2H); 4.25 (q,2H); 5.85 (tt,lH); 6.72 (bs,
462
1H) ; 6.82 (bs,lH); 6.90-7.35 (c,3H); 7.50 (bs,lH) 1.19 (t,3H); 2.20 (s,3H); 2.28 (s,3H); 2.97 (s,3H); 3.35 (bq,2H); 4.25 (q,2H); 5.85 (tt,lH); 6.72 (bs,
61 446
1H) ; 6.82 (bs,lH); 6.95-7.35 (c,3H); 7.50 (bs,lH)
1.19 (t,3H); 2.20 (s,3H); 2.28 (s,3H); 2.98 (s,3H); 3.37 (bq,2H); 5.85 (tt,lH); 6.72 (bs,lH); 6.82
68 415
(bs,lH); 7.10-7.90 (c,4H)
1.19 (t,3H); 1.50-2.0 (m, 8H) ; 2.20 (s,3H); 2.28 (s,3H); 2.98 (s,3H); 3.37 (bq, 2H); 4.80 (m, 1H) ; 6.72
86 382
(bs,lH); 6.83 (bs,lH); 6.9-7.35 (c,4H); 7.50 (bs,lH)
0.35 (m,2H); 0.65 (m,2H); 1.19 (t,3H); 1.30 (m, 1H) ; 2.20 (s,3H); 2.28 (s,3H); 2.98 (s,3H); 3.37 (bq,2H);
92 368
4.90 (s,2H); 6.72 (bs,lH); 6.82 (bs,lH); 6.9-7.35 (c, 4H); 7.50 (bs,lH)
EX7AMPLE 9
Determination of the fungicidal activity in preventive application (5 days) against Erysiphe gramlnls on wheat .
Leaves of wheat plants of the Salgemma variety, grown in pots in a conditioned environment kept at 20°C and 70% of relative humidity (R.H.), were treated by spraying on both sides of the leaves with the compounds under examination, dispersed in hydroacetonic solu¬ tions at 20% by volume of acetone.
After remaining 5 days in a conditioned environment, the plants were infected under dry conditions by shaking over them, in order to distribute the inoculum, plants previously infected by Erysiphe graminis .
The plants were then maintained in the same cell, in a humidity-saturated environment and at a tempera¬ ture ranging from 18 to 24°C for 12 days. At the end of this period, the external symptoms of the pathogen appeared and it was therefore possible to proceed with the evaluation of the intensity of the in¬ fection, on both the parts treated directly with the products (T) , and also on the parts which had developed during the test (NT) , by means of a visible percentage evaluation scale of the area of affected leafs; the scale comprises, as extremes, the value 100 (healthy plant) and the value 0 (completely infected plant) .
All the compounds N. 1-107 showed a full activity
(100%) at a dose of 500 p.p.m
At the same time, the phytotoxicity was evaluated (percentage of leaf necrosis) induced on the wheat plants by the application of the products: in this case, the evaluation scale varies from 0 (completely healthy plant) to 100 (completely necrotized plant) .
Table 4 shows the results obtained by effecting the test described with compounds N. 1, 2, 15, 19 and 23, compared with the following reference products de- scribed in Table 1 of WO 00/46184:
N, N-dimethyl-N' - [ 4- ( 3-trifluoromethylphenoxy) -2,5- xylyl ] -formamidine (compound N. 1: CR-1);
N, N-dimethyl-N' - [4- (3-trifluoromethylphenylthio) -2, 5- xylyl ] -formamidine (compound N. 4: CR-2);
N-ethyl-N-methyl-N' - [4- ( 3-trifluoromethylphenoxy) -2, 5- xylyl ] formamidine (compound N. 45: CR-3);
N, N-dimethy1-N' - [ 4- ( 3-trifluoromethoxyphenoxy) -2,5- xylyl ] formamidine (compound N. 190: CR-4);
N, N-dimethy1-N' -{4- [3- (2, 2, 2-trifluoroethoxy) phenoxy
2 , 5-xylyl } formamidine (compound N. 359: CR-5)
Table 4
Figure imgf000044_0001
The compounds N. 1, 2, 15, 19 and 23 proved to be less phytotoxic and/or more active with respect to the reference products. EXAMPLE 10
Determination of the fungicidal activity in preventive application (5 days) against Puccinia recondita on wheat .
Leaves of wheat plants of the Salgemma variety, grown in pots in a conditioned environment kept at 20°C and 70% of relative humidity (R.H.), were treated by spraying on both sides of the leaves with the compounds under examination, dispersed in hydroacetonic solutions at 20% by volume of acetone.
After remaining 5 days in a conditioned environment, the plants were sprayed on both sides of the leafs with an aqueous suspension of conidia of Puccinia recondita (2 mg of inoculum per 1 ml of solution for infection) .
After being sprayed, the plants were kept in a hu¬ midity-saturated environment at a temperature ranging from 18 to 24°C for the incubation period of the fungus (1 day) .
After this period, the plants were put in a green¬ house with R.H. of 70% and at a temperature of 18-24 °C for 14 days.
At the end of this period, the external symptoms of the pathogen appeared and it was therefore possible to proceed with the evaluation of the intensity of the in- fection, on both the parts treated directly with the products (T) , and also on the parts which had developed during the test (NT) , by means of a visible percentage evaluation scale of the area of affected leafs; the scale comprises, as extremes, the value 100 (healthy plant) and the value 0 (completely infected plant) .
All the compounds N. 1-107 showed a full activity (100%) at a dose of 500 p.p.m
At the same time, the phytotoxicity was evaluated (percentage of leaf necrosis) induced on the wheat plants by the application of the products: in this case, the evaluation scale varies from 0 (completely healthy plant) to 100 (completely necrotized plant) .
Table 5 shows the results obtained by effecting the test described with compounds N. 1, 2, 15, 19 and 23, compared with the following reference products de¬ scribed in Table 1 of WO 00/46184:
N, N-dimethyl-N' - [ 4- ( 3-trifluoromethylphenoxy) -2,5- xylyl ] -formamidine (compound N. 1: CR-1) ;
N, N-dimethyl-N' - [4- (3-trifluoromethylphenylthio) -2, 5- xylyl ] -formamidine (compound N. 4: CR-2) ;
N-ethyl-N-methyl-N' - [4- ( 3-trifluoromethylphenoxy) -2, 5- xylyl ] formamidine (compound N. 45: CR-3) ;
N, N-dimethyl-N' - [ 4- ( 3-trifluoromethoxyphenoxy) -2,5- xylyl ] formamidine (compound N. 190: CR-4) ; N, N-dimethy1-N' -{4- [3- (2, 2, 2-trifluoroethoxy) phenoxy] - 2 , 5-xylyl } formamidine (compound N. 359: CR-5)
Table 5
Figure imgf000047_0001
The compounds N. 1, 2, 15, 19 and 23 proved to be less phytotoxic and/or more active with respect to the reference products.

Claims

1) Phenylamidines having general formula (I) :
Figure imgf000048_0001
(I)
wherein
R represents a phenyl, pyridyl, pyrimidyl, pyrazyl or pyridazyl group, all groups substituted by at least a substituent selected from C1-C6 polyfluoroalkoxy con¬ taining at least one hydrogen atom, C1-C6 polyfluoroal- kylthio containing at least one hydrogen atom, C3-C6 cycloalkyl, C3-C6 halocycloalkyl , C3-C6 cycloalkoxy, C3- C6 halocycloalkoxy, C -C8 cycloalkylalkoxy, C -C8 halo- cycloalkylalkoxy; said groups phenyl, pyridyl, pyrimidyl, pyrazyl or pyridazyl being optionally sub¬ stituted by one or two further substituents , equal to or different from each other, selected from halogen atom, C1-C6 alkyl, C1-C6 haloalkyl;
Ri represents C2-C6 alkyl;
R2 represents C1-C6 alkyl;
or Ri and R2, together with the N atom to which they are bound, form a heterocyclic ring containing from 4 to 7 atoms, optionally substituted by halogen atoms;
R.3 and R , equal to or different from each other, represent a hydrogen atom, a halogen atom, a C1-C6 al- kyl, a C1-C6 alkoxy, a C1-C6 haloalkoxy, a CF3 group, a CF2H group, a CFH2 group, a cyano group.
2) The phenylamidines according to claim 1, wherein:
- R represents a phenyl, pyridyl, pyrimidyl, pyrazyl or pyridazyl group, all groups substituted by at least a substituent selected from difluoromethoxy, 2,2,2- trifluoroethoxy, 1 , 1 , 2 , 2-tetrafluoroethoxy, 2,2,3,3- tetrafluoropropoxy, 2,2,3,3, 3-pentafluoropropoxy,
2,2,3,4,4, 4-hexafluorobutoxy, 2, 2, 3, 3, 4, 4, 5, 5-octa- fluoropentoxy, cyclopentoxy, cyclohexyloxy, cyclopro- pylmethoxy or cyclohexylmethoxy; said phenyl, pyridyl, pyrimidyl, pyrazyl or pyridazyl group being optionally substituted by one or two further substituents , equal to or different from each other, selected from a fluo¬ rine atom, a chlorine atom, methyl or trifluoromethyl ; - Ri represents ethyl, n-propyl, isopropyl;
- R2 represents methyl;
or Ri and R2, together with the N atom to which they are bound, represent a pyrrolidyl, piperidyl or morpholyl group;
- R3 and R represent methyl. 3) The phenylamidines according to claim 1, selected from compounds having general formula (I) wherein:
- R represents a phenyl group substituted by at least a substituent selected from difluoromethoxy, 2,2,2- trifluoroethoxy, 1 , 1 , 2 , 2-tetrafluoroethoxy, 2,2,3,3- tetrafluoropropoxy, 2,2,3,3, 3-pentafluoropropoxy,
2,2,3,4,4, 4-hexafluorobutoxy, 2, 2, 3, 3, 4, 4, 5, 5-octa- fluoropentoxy, cyclopentoxy, cyclohexyloxy, cyclopro- pylmethoxy or cyclohexylmethoxy; said phenyl group be- ing optionally substituted by one or two further sub- stituents, equal to or different from each other, se¬ lected from a fluorine atom, a chorine atom, methyl or trifluoromethyl ;
- Ri represents ethyl, n-propyl, isopropyl;
- R2 represents a methyl;
or Ri and R2, together with the N atom to which they are bound, represent a pyrrolidyl, piperidyl or morpholyl- group;
- R3 and R represent methyl.
4) Fungicidal compositions comprising one or more compounds having formula (I), according to any of the claims from 1 to 3, a solvent and/or a solid or liquid diluent, optionally a surfactant.
5) The compositions according to claim 4, also comprising active principles compatible with the com- pounds having general formula (I), selected from fungi¬ cides other than the compounds having general formula (I), phytoregulators , antibiotics, herbicides, insecti¬ cides, fertilizers and/or mixtures thereof, antifreeze agents, adhesion agents.
6) The compositions according to claim 4 or 5, wherein the concentration of compounds having general formula (I) ranges 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.
7) Use of phenylamidines having general formula (I) :
Figure imgf000051_0001
(I)
wherein :
R represents a phenyl, pyridyl, pyrimidyl, pyrazyl or pyridazyl group, all groups substituted by at least a substituent selected from C1-C6 polyfluoroalkoxy con¬ taining at least one hydrogen atom, C1-C6 polyfluoroal- kylthio containing at least one hydrogen atom, C3-C6 cycloalkyl, C3-C6 halocycloalkyl , C3-C6 cycloalkoxy, C3- C6 halocycloalkoxy, C -C8 cycloalkylalkoxy, C -C8 halo- cycloalkylalkoxy; said groups phenyl, pyridyl, pyrimidyl, pyrazyl or pyridazyl being optionally sub¬ stituted by one or two further substituents , equal to or different from each other, selected from halogen atom, C1-C6 alkyl, C1-C6 haloalkyl;
Ri represents C2-C6 alkyl;
R2 represents C1-C6 alkyl;
or Ri and R2, together with the N atom to which they are bound, form a heterocyclic ring containing from 4 to 7 atoms, optionally substituted by halogen atoms;
R3 and R4, equal to or different from each other, represent a hydrogen atom, a halogen atom, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, a CF3 group, a CF2H group, a CF¾ group, a cyano group,
for the control of phytopatogenic fungi of agricultural crops .
8) Use of the compounds according to any of the claims 2-3, for the control of phytopatogenic fungi in agricultural crops.
9) Use of the compositions according to any of the claims 4-6 for the control of phytopatogenic fungi in agricultural crops.
10) Use according to any of the claims from 7 to 9, for the control of phytopatogenic fungi belonging to the group of Basidiomycetes , Ascomycetes, Deuteromy- cetes or imperfect fungi, Oomycetes: Puccinia spp., Ustilago spp., Tilletia spp., Uromyces spp., Phakopsora spp., Rhizoctonia spp., Erysiphe spp., Sphaerotheca spp., Podosphaera spp., Uncinula spp., Helminthospo- rium spp., Rhynchosporium spp., Pyrenophora spp., Moni- linia spp., Sclerotinia spp., Septoria spp. {Mycosphae- rella spp.), Venturia spp., Botrytis spp., Alternaria spp., Fusarium spp., Cercospora spp., Cercosporella herpotrichoides , Colletotrichum spp., Pyricularia oryzae, Sclerotium spp., Phytophtora spp., Pythium spp., Plasmopara viticola, Peronospora spp., Pseudoper- onospora cubensis, Bremia lactucae .
11) Use according to any of the claims from 7 to 9, wherein the agricultural crops are cereals, fruit trees, citrus trees, leguminous plants, horticultural plants, cucurbitaceae, oleaginous plants, tobacco, cof¬ fee, tea, cacao, sugar beet, sugar cane, cotton.
12) Use according to any of the previous claims from 7 to 9 for the control of Plasmopara viticola on vines; Phytophtora infestans and Botrytis Cinerea on tomatoes; Puccinia recondita r Erysiphe graminis , Helminthosporium teres, Septoria nodorum and Fusarium spp. on cereals; Phakopsora pachyrhizi on soybean; Uromyces Appendicula- tus on beans; Venturia inaequalis on apple trees; Sphaerotheca fuliginea on cucumbers.
13) Use of the compounds according to any of the claims from 1 to 3, or compositions according to any of the claims from 4 to 6, for the control of bacteria and phytopatogenic viruses.
14) A method for controlling phytopathogenic fungi in agricultural crops, which consists in applying ef¬ fective dosages of compounds according to any of the claims 1-3, in amounts ranging from 10 g to 5 kg per hectare of agricultural crop.
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