Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • 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
  • C07D239/26—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
• • 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
  • A01N37/36—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 at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
• • 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
  • A01N37/36—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 at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
  • A01N37/38—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 at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
• • 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
  • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
  • A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
• • 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
  • A01N49/00—Biocides, pest repellants or attractants, or plant growth regulators, containing compounds containing the group, wherein m+n>=1, both X together may also mean —Y— or a direct carbon-to-carbon bond, and the carbon atoms marked with an asterisk are not part of any ring system other than that which may be formed by the atoms X, the carbon atoms in square brackets being part of any acyclic or cyclic structure, or the group, wherein A means a carbon atom or Y, n>=0, and not more than one of these carbon atoms being a member of the same ring system, e.g. juvenile insect hormones or mimics thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
  • C07C251/32—Oximes
  • C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
  • C07C251/60—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by carboxyl groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C255/00—Carboxylic acid nitriles
  • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C255/57—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and carboxyl groups, other than cyano groups, bound to the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
  • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
  • C07C69/734—Ethers

Definitions

• This invention relates to strobilurin analogue compounds.
• the invention relates to strobilurin analogue compounds with high fungicidal activity, their preparation process and their use in agriculture for controlling phytopathogenic fungi .
• Strobil urines are secondary metabolites isolated from certain
• Basidomycetes strains which are characterised by the presence of a 1-methoxycarbonyl-2-methoxyethen-1-yl group and are able to inhibit itochondrial respiration.
• the compounds of the present invention are synthetic analogues of said strobilurins.
• - Ri represents a linear or branched Ci-C ⁇ fluoroalkyl group; or a linear or branched Ci-C ⁇ alkyl group;
• R 2 represents a hydrogen atom; a linear or branched Ci-C ⁇ al kyl or hal oal kyl group ; a l i near or branched C, -C , al koxy or hal oal koxy
• I 0 group a linear or branched C -C carboalkoxy group; a nitrile group.
• Tox represents a group of general formula (Ila) or (lib):
• Y represents an oxygen atom; or a -N(R6)- group
• R' and R" which can be equal or different, represent a hydrogen atom; or a linear or branched C-i-C ⁇ alkyl group;
• R3 and R 4 which can be equal or different, represent a linear or branched Ci-C ⁇ alkyl or haloalkyl group
• Rs and Re which can be equal or different, represent a hydrogen atom; or a linear or branched Ci-C ⁇ alkyl or haloalkyl group;
• K represents a chain of general formula (Ilia):
• Ri represents a linear or branched Ci-C ⁇ fluoroalkyl group
• R7 represents a linear or branched Ci-C ⁇ alkyl or haloalkyl group; a linear or branched Ci-Ce alkoxy or haloalkoxy group; a linear or branched C1-C6 thioalkyl or halothioalkyl group; a C3-C9 cycloalkyl group; a cyano group; a linear or branched C2-C10 carboalkoxy group; G3 and G4, which can be equal or different, represent a hydrogen atom; a halogen atom chosen from fluorine, chlorine and bromine; a linear or branched Ci-C ⁇ alkyl or haloalkyl group; X represents a phenyl group; a naphthyl group; a penta- or hexa-atomic aromatic heterocyclic group containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur;
• the compounds of general formula (I) can present geometrical isomerisms.
• the first isomerism relates to the double bond explicitly represented in formula (I).
• the second isomerism relates to the double bond present in the Tox group when said group is represented by the aforesaid general formula (Ha). It is therefore within the spirit of the present invention to consider both isomerically pure compounds of general formula (I) and mixtures thereof in any proportion.
• Ci-C ⁇ fluoroalkyl groups are: fluoromethyl , difluoromethyl , trifluoro ethyl , 2,2,2- trifluoroethyl , 2,2,3,3-tetrafluoropropyl , 2,2,3,3,3- pentafluoropropyl , etc.
• Ci-C ⁇ alkyl or haloalkyl groups are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl , s-pentyl , neo-pentyl , fluoromethyl , difluoromethyl , trifluoromethyl , 2,2,2-trifluoroethyl , 1,1 ,2,2-tetrafluoroethyl , trichloromethyl , 2,2,2-trichloroethyl , 2, 2, 3, 3-tetrafluoropropyl , 2,2,3,3,3-pentafluoropropyl , 2,2,2-trichloro-1 , 1-difluoroethyl , etc.
• Exampl es of l i near or branched Ci-C ⁇ al koxy or haloal koxy groups are : methoxy , ethoxy , t ri f l uoromethoxy , 1 , 1 , 2 , 2-tet raf l uoroethoxy , 2,2,2-trifluoroethoxy, 3,3,3,2,2-pentaf1 uoropropyloxy , 2,2,2- trichloro-1 , 1-di fluoroethoxy , etc.
• Ci-C ⁇ thioalkyl or halothioalkyl groups are: thiomethyl, thioethyl, trifluorothiomethoxy, 1,1,2,2- tetrafluorothioethoxy, etc.
• C3-C9 cycloalkyl groups are: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl , etc.
• linear or branched C2-C10 carboalkoxy groups are: carboxymethyl, carboxyethyl , carboxyisopropyl , etc.
• penta- or hexa-atomic aromatic heterocyclic groups containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur and benzocondensed penta- or hexa-atomic aromatic heterocyclic groups containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur are: pyrrole, imidazole, pyrazole, triazole, tetrazole, isoxazole, benzoisoxazole, oxazole, thiazole, isothiazole, benzothiazole, pyridine, pyrazine, pyrimidine, pyridazine, furan, benzofuran, thiophene, benzothiophene, benzoxazole, indole, etc.
• Examples of penta- or hexa-atomic aromatic heterocycloxy groups containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur, and benzocondensed penta- or hexa-atomic aromatic heterocycloxy groups containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur are: pyridoxy, pyrimidoxy, benzoxazolyloxy, benzothiazolyloxy, etc.
• Compounds of general formula (I) not illustrated in the examples but equally interesting for their fungicidal activity are:
• E E-2-(4-chlorophenyl )-1-( 1-methoxycarbonyl-2-methoxyethen-1- yl )-1-chloroethene;
• the compounds of general formula (I) of the present invention can be prepared by various synthetic paths, some of which are illustrated in the ensuing Schemes A-H in which, if not otherwise stated, the symbols used assume the meanings defined heretofore for the compounds of general formula (I). For greater clarity, all the preparation methods for said compounds are illustrated by the synthesis of particular cases of the compounds of general formula (I), the described method being however generally applicable to all compounds of general formula (I), with only those exceptions stated appropriately in the description.
• the compounds of general formula (I) can be conveniently obtained, for example, by condensation between an organic zinc of general formula (a2) or (a3) and a suitable compound of general formula
• Q2 represents a halogen atom chosen from chlorine, bromine and iodine.
• the organic zinc of general formula (a2) can be conveniently prepared starting from a compound of general formula (a4) as described, for example, in "Journal Organic Chemistry” (1996), vol . 61 , pp. 3200-3204.
• the compounds of general formula (a1) can be prepared, for example, as described in “Synlett” (1995), pp. 32-33.
• the organic zinc of general formula (a3) can be prepared by reacting a compound of general formula (a1) with a Zn/Ag mixture, prepared as described for example in "Tetrahedron Letters” (1981), vol. 22, pp.
• a chelating agent such as N,N,N' ,N'-tetramethyl-1 ,2-diaminoethane
• a dipolar aprotic solvent such as dimethyl formamide (DMF) or n-methyl-pyrrol idone (NMP), or an ether solvent such as tetrahydrofuran (THF).
• DMF dimethyl formamide
• NMP n-methyl-pyrrol idone
• THF tetrahydrofuran
• the organic zinc compounds of general formula (a2) and (a3) are reacted with the compounds of general formula (a1) and (a4) respectively, in the presence of a palladium catalyst or a precursor thereof, known in the literature.
• haloalkane of general formula (d) can be prepared for example by the procedure illustrated in the following Scheme D.
• the haloalkane 1 , 1 , 1-tribromo-2,2,2-trifluoroethane of formula (d1) is added, for radical reaction, to an alkene of formula (d2), in the presence of copper salts or of a radical inhibitor such as dibenzoylperoxide or azoisobutyronitrile (AIBN), to obtain the adduct of formula (d) in the case in which R 2 , in general formula (d), represents a hydrogen atom.
• a radical inhibitor such as dibenzoylperoxide or azoisobutyronitrile (AIBN)
• the haloalkane 1 , 1 , 1-trichloro-2,2,2-trif luoroethane of formula (e1) is reacted with zinc (Zn) in anhydrous dimethyl formamide (DMF), after which the suitable cinnamaldehyde of general formula (e2) and acetic anhydride are added, operating at a temperature of between 20°C and 100°C.
• the zinc used could be activated by adding a catalytic quantity of silver salts as described for example in "Journal Organic Chemistry” (1996), vol. 61, pp. 3200- 3204.
• haloalkane of formula (e1) and the cinnamaldehyde of general formula (e2) are commercially available products, and can also be easily prepared by the processes described in the known art.
• the compounds of general formula (I) of the present invention can also be prepared by the procedure illustrated in the following Scheme F. SCHEME F
• the compound of general formula (f1) obtainable as described for example in "Journal of American Chemical Society” (1951), vol. 73, pp. 3648-3686 and in “Synthesis” (1985), pp. 850-855, is reacted with the phosphorus ilide of general formula (f3), in which Ph represents the phenyl group and J represents the -K- ⁇ - group, if compatible with the reaction conditions. If not, then the compound of general formula (f1) is reacted with a precursor ilide of the phosphorus ilide of general formula (f3).
• the phosphorus ilide of general formula (f3) is a commercially available product, and can also be easily prepared by the processes described in the known art.
• the product of general formula (g2) is a commercially available product, and can also be easily prepared by the processes described in the known art.
• the mesylate (h3) is then reacted, for example, with a group of general formula H-G2-X in which G2 represents an oxygen or sulphur atom, or a previously described group of general formula (Vd), in presence of an inorganic base, as for example potassium carbonate, in the presence of a dipolar aprotic solvent such as dimethyl formamide (DMF), or an ether solvent such as tetrahydrofuran (THF)
• a dipolar aprotic solvent such as dimethyl formamide (DMF), or an ether solvent such as tetrahydrofuran (THF)
• DMF dimethyl formamide
• THF tetrahydrofuran
• the compounds of general formula (I) possess particularly high fungicidal activity against those phytopathogenic fungi which attack vines, sugar beet, cereals, Cucurbitaceae and fruit trees.
• plant diseases which can be combated using the compounds of general formula (I) according to the present invention:
• the compounds of general formula (I) are able to provide a fungicidal action of both curative and preventive character, and in addition they demonstrate little or no phytotoxicity.
• fungicidal compositions containing one or more compounds of general formula (I), possibly as a mixture of isomers, as the active substance.
• compositions can be applied to any part of the plant, for example on leaves, stems, branches and roots, or on the seeds themselves before sewing, or even on the soil in which the plant grows .
• compositions used can be in the form of dry powder, wettable powder, emulsifiable concentrates, icroemulsions, paste, granulates, solutions, suspensions etc.
• the choice of the type of composition depends on the specific use.
• the compositions are prepared in known manner, for example by diluting or dissolving the active substance with a solvent medium and/or a solid diluent, possible with surfactants present.
• the following can be used as solid diluents or supports: silica, kaolin, bentonite, talc, kieselguhr, dolomite, calcium carbonate, magnesia, chalk, clays, synthetic silicates, attapulgite, sepiol ite.
• suitable liquid diluents include various solvents, for example aromatic solvents (xylenes or alkyl-benzene mixtures), chloroaro atic solvents (chlorobenzene) , paraffins (petroleum fractions), alcohols (methanol, propanol , butanol , octanol , glycerin), amines, amides (N,,N-dimethyl formamide, N- methylpyrrol idone) , ketones (cyclohexanone, acetone, acetophenone, isophorone, ethylamylketone) , esters (isobutyl acetate).
• aromatic solvents xylenes or alkyl-benzene mixtures
• chloroaro atic solvents chlorobenzene
• paraffins petroleum fractions
• alcohols methanol, propanol , butanol , octanol , g
• Usable surfactants include sodium, calcium, triethanolamine or triethyla ine salts, alkyl sulphonates, alkylarylsulphonates, polyethoxylated alkylphenols, fatty alcohols condensed with ethylene oxide, polyoxyethylated fatty acids, polyoxyethylated sorbitol esters, 1 igninsulphonates.
• compositions can also contain special additives for particular purposes, for example adhesive-forming additives such as gum arabic, polyvinyl alcohol, polyvinylpyrrol idone.
• adhesive-forming additives such as gum arabic, polyvinyl alcohol, polyvinylpyrrol idone.
• other compatible active principles can be added to the compositions of the present invention, such as fungicides, phytoregulators, antibiotics, herbicides, insecticides, fertil izers.
• fungicides which can beincluded in the composition of the invention are alanicarb, ampropylfos, anilazine, azaconazole, azoxyst robin, BAS 490 F, BAY KTU 3616 benalaxyl, benomyl , bilosazol, binapacryl , bitertanol, blasticidin S, bromoconazole, bupirimate, butenaclor, buthiobate, captafol , captan, carbendazim, carbox, chinoethionat , chlorobenzothiazone, chloroneb, chlorothalonil , clozolinate, clozylacon, copper salts, cyclohexyl imide, cymoxanil, cyproconazole, cyprofurane, cyprodinyl, CGA 245 704, diclofluanid, dichlone, diclobutrazole
• the active substance concentration in said compositions can vary within a wide range, depending on the active compound, the crop, the pathogen, the environmental conditions and the type of formulation used.
• the active substance concentration varies between 0.1% and 95%, preferably between 0.5% and 90%.
• the ensuing examples are given as non-limiting illustration of the present invention.
• N,N,N' ,N'-tetramethyl-1 ,2-diaminoethane in 5 cm 3 of tetrahydrofuran is added.
• EXAMPLE 3 Operating in a like manner to that described in Example 1, but starting from a 1 , 1-dihaloethene (prepared by the procedure described in "Synthesis” (1993), pp. 43-46), the following compounds are prepared: - E,E-2-(4-chlorophenyl )-1-(1-methoxycarbonyl-2-methoxyethen- - yl )-1-bromoethene (Compound No. 8);
• 0.124 cm 3 of trichloro—methylsilane are added to a suspension of 1.6 g of Zn/Ag in 8 cm 3 of anhydrous tetrahydrofuran. After 10 minutes at ambient temperature, a mixture of 2.3 g of methyl 3- methoxy-2-iodopropenoate and 1.5 cm 3 of N,N,N' ,N'-tetramethyl-1 ,2- diaminoethane in 4 cm 3 of tetrahydrofuran is added.
• the plants are maintained in a moisture-saturated environment at
• Leaves of cultigen Arna barley plants grown in pots in a conditioned environment (20 ⁇ 1°C, 70% relative humidity) are treated by spraying both sides of the leaves with Compounds 1-13 in a 20 vol% acetone/water solution.
• the plants were sprayed on both leaf sides with an aqueous suspension of Helminthosporium teres conidia (250000 conidia per cm 3 ). The plants are maintained in a moisture-saturated environment at
• the fungicidal activity is evaluated on a percentage evaluation scale ranging from 100
• Leaves of cultigen Dolcetto vines grown in pots in a conditioned environment (20 ⁇ 1°C, 70% relative humidity) are treated by spraying both sides of the leaves with Compounds 1-13 in a 20 vol% acetone/water solution.
• the plants were sprayed on both leaf sides with an aqueous suspension of Plasmopara viticola conidia (200000 conidia per cm 3 ). The plants are maintained in a moisture-saturated environment at
• the fungicidal activity is evaluated on a percentage evaluation scale ranging from 100

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