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WO1997007099A1 - Alpha-methoxymethylene or alpha-methoxyimino naphthylacetic acid derivatives and their use as fungicides - Google Patents

Alpha-methoxymethylene or alpha-methoxyimino naphthylacetic acid derivatives and their use as fungicides Download PDF

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WO1997007099A1
WO1997007099A1 PCT/GB1996/001948 GB9601948W WO9707099A1 WO 1997007099 A1 WO1997007099 A1 WO 1997007099A1 GB 9601948 W GB9601948 W GB 9601948W WO 9707099 A1 WO9707099 A1 WO 9707099A1
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optionally substituted
compounds
hydrogen
alkyl
compound
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Clive Leonard Cornell
David Eric Green
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Bayer CropScience Ltd Great Britain
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Agrevo UK Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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
    • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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 with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/335—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—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
    • 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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/53—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—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
    • 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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/55—Acids; Esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—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
    • 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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/57—Nitriles
    • 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
    • C07D239/28—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
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • 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
    • C07D241/12—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom

Definitions

  • This invention relates to compounds having fungicidal activity.
  • X and Y which are the same or different, are hydrogen, halogen, 0 optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkylalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted arylalkoxy, optionally substituted heteroarylalkoxy, 5 optionally substituted acyloxy, optionally substituted amino, acylamino, nitro, cyano, -C0 2 R 3 , -CONR 4 R 5 , or -COR 6 , except that X and Y are not both hydrogen; R 1 and R 2 , which are the same or different, are alkyl or fluoroalkyl; and R 3 , R 4 , R 5 and R 6 , which are the same or different, are
  • A is NH or O
  • X is N or CH
  • R 2 is hydrogen or alkyl
  • R is alkyl, cycloalkyl, phenyl, heterocyclyl or amino, each of which is optionally substituted, or is hydrogen;
  • R 21 has the same meaning as R 20 and may also be cyano; and
  • R 22 has the same meaning as R 20 and may aiso be -COR 20 .
  • Any alkyl group present in the molecule is preferably of 1 to 8 carbon atoms, especially of 1 to 6 carbon atoms, and particularly of 1 to 4 carbon atoms, and may be unsubstituted or substituted.
  • Any alkenyl or alkynyl group present in the molecule is preferably of 2 to 6 carbon atoms, for example allyl, vinyl or propargyl.
  • Any cycloalkyl or cycloalkenyl group present in the molecule is preferably of 3 to 7 carbon atoms.
  • heterocyclyl includes both aromatic and non-aromatic heterocyclyl groups.
  • Heterocyclyl groups are generally 5, 6 or 7-membered rings containing up to 4 hetero atoms selected from nitrogen, oxygen and sulfur.
  • Examples of heterocyclyl groups are furyl, thienyl, pyrrolyl, pyrrolinyl, pyrrolidinyl, imidazolyl, dioxolanyl, oxazolyl, thiazolyl, imidazolyl, imidazolinyl, imidazolidinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, pyranyl, pyridyl, piperidinyl, dioxanyl, morpholino, dithianyl, thiomorpholino, pyridazinyl, pyrimi
  • Substituents when present on any phenyl or heterocyclyl group may for example be halogen, cyano or nitro, acyl, O-acyl or a group T, OT or S(0) n T, where n is 0, 1 or 2 and T is optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted acyl, optionally substituted phenyl, optionally substituted heterocyclyl or optionally substituted amino or two adjacent groups on the ring together with the atoms to which they are attached form a carbocyclic or heterocyclic ring, which may be similarly substituted.
  • Substituents when present on any alkyl, alkenyl, alkynyl or cycloalkenyl moiety include halogen, cyano, optionally substituted alkoxy, optionally substituted alkylthio, hydroxy, nitro, optionally substituted amino, acyl, acyloxy, optionally substituted phenyl, optionally substituted heterocyclyl, optionally substituted phenoxy and optionally substituted heterocyclyloxy.
  • acyl includes the residue of sulfur and phosphorus-containing acids as well as carboxylic acids.
  • the aminooxymethyl group may be attached at the 5-, 6-, 7- or 8-position on the naphthalene ring, especially in the 7-position.
  • R 2 is hydrogen.
  • Preferred compounds are those where X is CH and A is 0 or X Is N and A is O or NH.
  • a preferred group of compounds are those where R 3 is heteroaryl, especially a nitrogen containing heteroaryl of 5 or 6 carbon atoms, e.g. pyridyl, and R 4 is hydrogen or alkyl, especially methyl.
  • the compounds of the invention also exist as E and Z isomers of the methyleneaminooxy group and the invention includes individual geometric isomers as well as mixtures of these.
  • the invention includes any compound of formula I and specifically exemplified.
  • the compounds of the invention have activity as fungicides, especially against fungal diseases of plants, e.g. mildews and particularly cereal powdery mildew (Erysiphe graminis) and vine downy mildew (Plasmopara viticola), rice blast (Pyricularia oryzae), cereal eyespot (Pseudocercosporella herpotrichoides), rice sheath blight (Pellicularia sasakii), grey mould (Botrytis cinerea), damping off
  • mildews and particularly cereal powdery mildew (Erysiphe graminis) and vine downy mildew (Plasmopara viticola), rice blast (Pyricularia oryzae), cereal eyespot (Pseudocercosporella herpotrichoides), rice sheath blight (Pellicularia sasakii), grey mould (Botrytis cinerea), damping off
  • fungi against which the compounds may be active include other powdery mildews, other rusts, and general pathogens of Deuteromycete, Ascomycete, Phycomycete and Basidomycete origin.
  • the invention thus also provides a method of combating fungi at a locus infested or liable to be infested therewith, which comprises applying to the locus a compound of formula I.
  • the invention also provides a fungicidal composition
  • a fungicidal composition comprising a compound of formula I in admixture with an agriculturally acceptable diluent or carrier.
  • composition of the invention may of course include more than one compound of the invention.
  • composition can comprise one or more additional active ingredients, for example compounds known to possess plant-growth regulant, herbicidal, fungicidal, insecticidal or acaricidal properties.
  • additional active ingredients for example compounds known to possess plant-growth regulant, herbicidal, fungicidal, insecticidal or acaricidal properties.
  • the compound of the invention can be used in sequence with the other active ingredient.
  • the diluent or carrier in the composition of the invention can be a solid or a liquid optionally in association with a surface-active agent, for example a dispersing agent, emulsifying agent or wetting agent.
  • Suitable surface-active agents include anionic compounds such as a carboxylate, for example a metal carboxylate of a long chain fatty acid; an N-acylsarcosinate; mono- or di-esters of phosphoric acid with fatty alcohol ethoxylates or salts of such esters; fatty alcohol sulfates such as sodium dodecyl sulfate, sodium octadecyl sulfate or sodium cetyl sulfate; ethoxylated fatty alcohol sulfates; ethoxylated alkylphenol sulfates; lignin sulfonates; petroleum sulfonates; alkyl-aryl sulfonates such as alkyl-benzene s
  • butyl-naphthalene sulfonate salts of sulfonated naphthalene-formaldehyde condensates; salts of sulfonated phenol-formaldehyde condensates; or more complex sulfonates such as the amide sulfonates, e.g. the sulfonated condensation product of oleic acid and N-methyl taurine or the dialkyl sulfosuccinates, e.g. the sodium sulfonate of dioctyl succinate.
  • amide sulfonates e.g. the sulfonated condensation product of oleic acid and N-methyl taurine or the dialkyl sulfosuccinates, e.g. the sodium sulfonate of dioctyl succinate.
  • Nonionic agents include condensation products of fatty acid esters, fatty alcohols, fatty acid amides or fatty-alkyl- or alkenyl-substituted phenols with ethylene oxide, fatty esters of polyhydric alcohol ethers, e.g. sorbitan fatty acid esters, condensation products of such esters with ethylene oxide, e.g. polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, acetylenic glycols such as 2,4,7,9-tetramethyl-5-decyne-4,7-diol, or ethoxylated acetylenic glycols.
  • a cationic surface-active agent examples include, for instance, an aliphatic mono-, di-, or polyamine as an acetate, naphthenate or oleate; an oxygen-containing amine such as an amine oxide or polyoxyethylene alkylamine; an amide-linked amine prepared by the condensation of a carboxylic acid with a di- or polyamine; or a quaternary ammonium salt.
  • compositions of the invention can take any form known in the art for the formulation of agrochemicals, for example, a solution, a dispersion, an aqueous emulsion, a dusting powder, a seed dressing, a fumigant, a smoke, a dispersible powder, an emulsifiable concentrate or granules. Moreover it can be in a suitable form for direct application or as a concentrate or primary composition which requires dilution with a suitable quantity of water or other diluent before application.
  • An emulsifiable concentrate comprises a compound of the invention dissolved in a water-immiscible -solvent which is formed into an emulsion with water in the presence of an emulsifying agent.
  • a dusting powder comprises a compound of the invention intimately mixed and ground with a solid pulverulent diluent, for example, kaolin.
  • a granular solid comprises a compound of the invention associated with similar diluents to those which may be employed in dusting powders, but the mixture is granulated by known methods. Alternatively it comprises the active ingredient absorbed or adsorbed on a pre-granular diluent, for example. Fuller's earth, attapulgite or limestone grit.
  • Wettable powders, granules or grains usually comprise the active ingredient in admixture with a suitable surfactant and an inert powder diluent such as china clay.
  • Another suitable concentrate is a flowable suspension concentrate which is formed by grinding the compound with water or other liquid, a wetting agent and a suspending agent.
  • the concentration of the active ingredient in the composition of the present invention, as applied to plants is preferably within the range of 0.0001 to 1 .0 per cent by weight, especially 0.0001 to 0.01 per cent by weight.
  • the amount of active ingredient can vary widely and can be, for example, from 5 to 95 per cent by weight of the composition.
  • the compound is generally applied to seeds, plants or their habitat.
  • the compound can be applied directly to the soil before, at or after drilling so that the presence of active compound in the soil can control the growth of fungi which may attack seeds.
  • the active compound can be applied in any manner which allows it to be intimately mixed with the soil such as by spraying, by broadcasting a solid form of granules, or by applying the active ingredient at the same time as drilling by inserting it in the same drill as the seeds.
  • a suitable application rate is within the range of from 5 to 1000 g per hectare, more preferably from 10 to 500 g per hectare.
  • the active compound can be applied directly to the plant by, for example, spraying or dusting either at the time when the fungus has begun to appear on the plant or before the appearance of fungus as a protective measure.
  • the preferred mode of application is by foliar spraying. It is generally important to obtain good control of fungi in the early stages of plant growth as this is the time when the plant can be most severely damaged.
  • the spray or dust can conveniently contain a pre- or post-emergence herbicide if this is thought necessary.
  • a suitable rate of application is from 0.025 to 5 kg per hectare, preferably from 0.05 to 1 kg per hectare.
  • the compounds of the invention where A is -0- may be prepared in 3 variety of ways, for example by reacting a compound of formula II:
  • the compounds of formula III may be prepared by reacting the corresponding compounds of formula IV:
  • R is as defined hereinbefore, either with methyl formate in the presence of a base, and then with dimethyl sulfate in the presence of a base, to give the desired compounds where X is CH, or with an alkyl nitrite in the presence of a base, and then with dimethyl sulfate in the presence of a base, to give the desired compounds where X is N.
  • the compounds of formula I in which A is 0 and X is N can be prepared in two steps from compounds of formula I where A is O and X is CH by ozonolysis followed by treatment of the resulting keto ester with methoxylamine hydrochloride.
  • the compounds of formula I in which A is NH and X is N may be prepared from the corresponding compounds of formula I in which A is 0 and X is N by reaction thereof with methylamine in a suitable solvent, e.g. methanol, to give the desired compounds.
  • the compounds of formula I in which A is NH and X is CH may be prepared from the corresponding compounds of formula I in which A is 0 and X is CH by converting the -C0 2 CH 3 group to -C0 2 H by means of lithium iodide in a suitable solvent medium, e.g. dimethylformamide, followed by chlorination using thionyl chloride, and reaction of the compound so formed with methylamine by methods known per se to give the desired compound.
  • a suitable solvent medium e.g. dimethylformamide
  • the invention is illustrated in the following Examples. Structures of isolated novel compounds were confirmed by appropriate analyses, e.g. 1 H nmr, mass spectrometry and IR spectroscopy.
  • Methyl (E)-3-methoxy-2-f7-f 1 -(2-pyridyl)ethylideneaminooxymethyll-1 -naphthyl1 acrylate (Compound 1 )
  • a solution of methyl (E)-2-(7-bromomethyl-1 -naphthyl)-3-methoxyacrylate ( 1 g), 2-acetylpyridine oxime (0.41 g) and tetrabutylammonium hydrogen sulfate ( 1 .32 g) in dichloromethane (3 ml) and 2M sodium hydroxide (3 ml) was vigorously stirred for 4 hours at room temperature.
  • Test Example Compounds are assessed for activity against one or more of the following: Phytophthora infestans: late tomato blight Plasmopara viticola: vine downy mildew Erysiphe graminis f. sp. hordei: barley powdery mildew Erysiphe graminis f. sp. tritici: wheat powdery mildew Pyricularia oryzae: rice blast
  • Botrytis cinerea grey mould
  • Venturia inaequalis apple scab Leptosphaeria nodorum: glume blotch
  • Aqueous solutions or dispersions of the compounds at the desired concentration, including a wetting agent, were applied by spray or by drenching the stem base of the test plants, as appropriate. Plants or plant parts were then inoculated with appropriate test pathogens and kept under controlled environment conditions suitable for maintaining plant growth and development of the disease. After an appropriate time, the degree of infection of the affected part of the plant was visually estimated. Compounds were considered active if they gave greater than 50% control of the disease at a concentration of 500 ppm (w/v) or less.
  • Compound 5 showed activity against Botrytis cinerea
  • Compound 1 -5 showed activity against Venturia inaequalis; Compounds 5, 1 1 , 1 3, 1 4, 1 7, 1 8 , 21 -23, 28 and 29 showed activity against
  • Leptosphaeria nodorum Leptosphaeria nodorum.

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Abstract

Compounds of formula (I), where A is NH or O; X is N or CH; R2 is hydrogen or alkyl; R?3 and R4¿, which may be the same or different, are alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkoxy, alkylthio, phenyl or heterocyclyl, each of which is optionally substituted, hydrogen, cyano, a group -COR20 or a group -C(R?21)=N-OR22¿, with the proviso that R?3 and R4¿ are not simultaneously hydrogen; or R?3 and R4¿, together with the carbon atom to which they are attached, form an optionally substituted 5- to 7-membered ring optionally including one to three heteroatoms selected from N, O and S; R20 is alkyl, cycloalkyl, phenyl, heterocyclyl or amino, each of which is optionally substituted, or is hydrogen; R21 has the same meaning as R20 and may also be cyano; and R22 has the same meaning as R20 and may also be -COR20, have activity as fungicides.

Description

ALPHA-METHOXYMETHYLENE OR ALPHA-METHOXYIMINO NAPHTHYLACETIC ACID DERIVATIVES AND THEIR USE AS FUNGICIDES
5 This invention relates to compounds having fungicidal activity.
In EP 267734 there are described compounds of formula
Figure imgf000003_0001
wherein X and Y, which are the same or different, are hydrogen, halogen, 0 optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkylalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted arylalkoxy, optionally substituted heteroarylalkoxy, 5 optionally substituted acyloxy, optionally substituted amino, acylamino, nitro, cyano, -C02R3, -CONR4R5, or -COR6, except that X and Y are not both hydrogen; R1 and R2, which are the same or different, are alkyl or fluoroalkyl; and R3, R4, R5 and R6, which are the same or different, are hydrogen, alkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted aralkyl, or cycloalkylalkyl. 0
In EP 267734 no compounds are disclosed in which X or Y is a substituted or unsubstituted aminooxymethyl group. We have now found certain such compounds have particularly valuable fungicidal activity.
5 The invention provides compounds of formula
Figure imgf000003_0002
where:
A is NH or O;
X is N or CH;
R2 is hydrogen or alkyl; R and R4, which may be the same or different, are alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkoxy, alkylthio, phenyl or heterocyclyl, each of which is optionally substituted, hydrogen, cyano, a group -COR20 or a group -C(R21) = N-OR22, with the proviso that R3 and R4 are not simultaneously hydrogen; or R and R4, together with the carbon atom to which they are attached, form an optionally substituted 5- to 7-membered ring optionally including one to three heteroatoms selected from N, 0 and S;
20
R is alkyl, cycloalkyl, phenyl, heterocyclyl or amino, each of which is optionally substituted, or is hydrogen; R21 has the same meaning as R20 and may also be cyano; and R22 has the same meaning as R20 and may aiso be -COR20.
Any alkyl group present in the molecule is preferably of 1 to 8 carbon atoms, especially of 1 to 6 carbon atoms, and particularly of 1 to 4 carbon atoms, and may be unsubstituted or substituted.
Any alkenyl or alkynyl group present in the molecule is preferably of 2 to 6 carbon atoms, for example allyl, vinyl or propargyl.
Any cycloalkyl or cycloalkenyl group present in the molecule is preferably of 3 to 7 carbon atoms.
The term heterocyclyl includes both aromatic and non-aromatic heterocyclyl groups. Heterocyclyl groups are generally 5, 6 or 7-membered rings containing up to 4 hetero atoms selected from nitrogen, oxygen and sulfur. Examples of heterocyclyl groups are furyl, thienyl, pyrrolyl, pyrrolinyl, pyrrolidinyl, imidazolyl, dioxolanyl, oxazolyl, thiazolyl, imidazolyl, imidazolinyl, imidazolidinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, pyranyl, pyridyl, piperidinyl, dioxanyl, morpholino, dithianyl, thiomorpholino, pyridazinyl, pyrimidinyl, pyrazinyl, piperazinyl, triazinyl, thiazolinyl, benzimidazolyl, tetrazolyl, benzoxazolyl, imidazopyridinyl, 1 ,3-benzoxazinyl, 1 ,3-benzothiazinyl, oxazolopyridinyl, benzofuranyl, quinolinyl, quinazolinyl, quinoxalinyl, sulfolanyl, dihydroquinazolinyl, benzothiazolyl, phthalimido, benzofuranyl, azepinyl, oxazepinyl, thiazepinyl, diazepinyl and beπzodiazepinyl.
Substituents when present on any phenyl or heterocyclyl group may for example be halogen, cyano or nitro, acyl, O-acyl or a group T, OT or S(0)nT, where n is 0, 1 or 2 and T is optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted acyl, optionally substituted phenyl, optionally substituted heterocyclyl or optionally substituted amino or two adjacent groups on the ring together with the atoms to which they are attached form a carbocyclic or heterocyclic ring, which may be similarly substituted.
Substituents, when present on any alkyl, alkenyl, alkynyl or cycloalkenyl moiety include halogen, cyano, optionally substituted alkoxy, optionally substituted alkylthio, hydroxy, nitro, optionally substituted amino, acyl, acyloxy, optionally substituted phenyl, optionally substituted heterocyclyl, optionally substituted phenoxy and optionally substituted heterocyclyloxy.
The term acyl includes the residue of sulfur and phosphorus-containing acids as well as carboxylic acids. Examples of acyl groups are thus -C( = 0)R5, -C( = 0)OR5, -C( = Y)NR5R6, -C( = 0)N(R5)OR6, -C( = 0)ONR5R6, -C( = 0)N(R5)NR6R7, -C( = 0)SR5, -C( = S)SR5, -S(0)pR5, -S( = 0)2OR5, -S( = 0)pNR5R6, -P( = Y)(OR5)(OR6), -C( = 0)-C( = 0)OR5, where R5, R6 and R7 which may be the same or different, are hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted phenyl or optionally substituted heterocyclyl or R6 and R7 together with the atom(s) to which they are attached can form a ring, p is 1 or 2 and Y is 0 or S.
The aminooxymethyl group may be attached at the 5-, 6-, 7- or 8-position on the naphthalene ring, especially in the 7-position.
It is generally preferred that R2 is hydrogen. Preferred compounds are those where X is CH and A is 0 or X Is N and A is O or NH.
A preferred group of compounds, are those where R3 is heteroaryl, especially a nitrogen containing heteroaryl of 5 or 6 carbon atoms, e.g. pyridyl, and R4 is hydrogen or alkyl, especially methyl.
The compounds of the invention exist as the E and Z isomers of the CH30-X = group and the invention includes individual isomers as well as mixtures of these, with the E-isomer -being preferred. Similarly, the compounds of the invention also exist as E and Z isomers of the methyleneaminooxy group and the invention includes individual geometric isomers as well as mixtures of these.
The invention includes any compound of formula I and specifically exemplified.
The compounds of the invention have activity as fungicides, especially against fungal diseases of plants, e.g. mildews and particularly cereal powdery mildew (Erysiphe graminis) and vine downy mildew (Plasmopara viticola), rice blast (Pyricularia oryzae), cereal eyespot (Pseudocercosporella herpotrichoides), rice sheath blight (Pellicularia sasakii), grey mould (Botrytis cinerea), damping off
(Rhizoctonia solani), wheat brown rust (Puccinia recondita), late tomato or potato blight (Phytophthora infestans), apple scab (Venturia inaequalis), glume blotch (Leptosphaeria nodorum). Other fungi against which the compounds may be active include other powdery mildews, other rusts, and general pathogens of Deuteromycete, Ascomycete, Phycomycete and Basidomycete origin.
The invention thus also provides a method of combating fungi at a locus infested or liable to be infested therewith, which comprises applying to the locus a compound of formula I.
The invention also provides a fungicidal composition comprising a compound of formula I in admixture with an agriculturally acceptable diluent or carrier.
The composition of the invention may of course include more than one compound of the invention. In addition the composition can comprise one or more additional active ingredients, for example compounds known to possess plant-growth regulant, herbicidal, fungicidal, insecticidal or acaricidal properties. Alternatively the compound of the invention can be used in sequence with the other active ingredient.
The diluent or carrier in the composition of the invention can be a solid or a liquid optionally in association with a surface-active agent, for example a dispersing agent, emulsifying agent or wetting agent. Suitable surface-active agents include anionic compounds such as a carboxylate, for example a metal carboxylate of a long chain fatty acid; an N-acylsarcosinate; mono- or di-esters of phosphoric acid with fatty alcohol ethoxylates or salts of such esters; fatty alcohol sulfates such as sodium dodecyl sulfate, sodium octadecyl sulfate or sodium cetyl sulfate; ethoxylated fatty alcohol sulfates; ethoxylated alkylphenol sulfates; lignin sulfonates; petroleum sulfonates; alkyl-aryl sulfonates such as alkyl-benzene sulfonates or iower alkylnaphthalene sulfonates, e.g. butyl-naphthalene sulfonate; salts of sulfonated naphthalene-formaldehyde condensates; salts of sulfonated phenol-formaldehyde condensates; or more complex sulfonates such as the amide sulfonates, e.g. the sulfonated condensation product of oleic acid and N-methyl taurine or the dialkyl sulfosuccinates, e.g. the sodium sulfonate of dioctyl succinate. Nonionic agents include condensation products of fatty acid esters, fatty alcohols, fatty acid amides or fatty-alkyl- or alkenyl-substituted phenols with ethylene oxide, fatty esters of polyhydric alcohol ethers, e.g. sorbitan fatty acid esters, condensation products of such esters with ethylene oxide, e.g. polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, acetylenic glycols such as 2,4,7,9-tetramethyl-5-decyne-4,7-diol, or ethoxylated acetylenic glycols.
Examples of a cationic surface-active agent include, for instance, an aliphatic mono-, di-, or polyamine as an acetate, naphthenate or oleate; an oxygen-containing amine such as an amine oxide or polyoxyethylene alkylamine; an amide-linked amine prepared by the condensation of a carboxylic acid with a di- or polyamine; or a quaternary ammonium salt. The compositions of the invention can take any form known in the art for the formulation of agrochemicals, for example, a solution, a dispersion, an aqueous emulsion, a dusting powder, a seed dressing, a fumigant, a smoke, a dispersible powder, an emulsifiable concentrate or granules. Moreover it can be in a suitable form for direct application or as a concentrate or primary composition which requires dilution with a suitable quantity of water or other diluent before application.
An emulsifiable concentrate comprises a compound of the invention dissolved in a water-immiscible -solvent which is formed into an emulsion with water in the presence of an emulsifying agent.
A dusting powder comprises a compound of the invention intimately mixed and ground with a solid pulverulent diluent, for example, kaolin.
A granular solid comprises a compound of the invention associated with similar diluents to those which may be employed in dusting powders, but the mixture is granulated by known methods. Alternatively it comprises the active ingredient absorbed or adsorbed on a pre-granular diluent, for example. Fuller's earth, attapulgite or limestone grit.
Wettable powders, granules or grains usually comprise the active ingredient in admixture with a suitable surfactant and an inert powder diluent such as china clay.
Another suitable concentrate is a flowable suspension concentrate which is formed by grinding the compound with water or other liquid, a wetting agent and a suspending agent.
The concentration of the active ingredient in the composition of the present invention, as applied to plants is preferably within the range of 0.0001 to 1 .0 per cent by weight, especially 0.0001 to 0.01 per cent by weight. In a primary composition, the amount of active ingredient can vary widely and can be, for example, from 5 to 95 per cent by weight of the composition. In the method of the invention the compound is generally applied to seeds, plants or their habitat. Thus, the compound can be applied directly to the soil before, at or after drilling so that the presence of active compound in the soil can control the growth of fungi which may attack seeds. When the soil is treated directly the active compound can be applied in any manner which allows it to be intimately mixed with the soil such as by spraying, by broadcasting a solid form of granules, or by applying the active ingredient at the same time as drilling by inserting it in the same drill as the seeds. A suitable application rate is within the range of from 5 to 1000 g per hectare, more preferably from 10 to 500 g per hectare.
Alternatively the active compound can be applied directly to the plant by, for example, spraying or dusting either at the time when the fungus has begun to appear on the plant or before the appearance of fungus as a protective measure. In both such cases the preferred mode of application is by foliar spraying. It is generally important to obtain good control of fungi in the early stages of plant growth as this is the time when the plant can be most severely damaged. The spray or dust can conveniently contain a pre- or post-emergence herbicide if this is thought necessary. Sometimes, it is practicable to treat the roots of a plant before or during planting, for example, by dipping the roots in a suitable liquid or solid composition. When the active compound is applied directly to the plant a suitable rate of application is from 0.025 to 5 kg per hectare, preferably from 0.05 to 1 kg per hectare.
The compounds of the invention where A is -0- may be prepared in 3 variety of ways, for example by reacting a compound of formula II:
Figure imgf000009_0001
where X and R2 are as defined hereinbefore with an oxime of formula R3R4C = N0H, where R3 and R4 are as defined hereinbefore, in the presence of a base, to give the desired compound. The compounds of formula II, which are themselves novel, may be prepared by subjecting the corresponding compounds of the formula III:
Figure imgf000010_0001
where X and R are as defined hereinbefore to the action of N-bromosuccinimide to give the desired compound.
In turn, the compounds of formula III may be prepared by reacting the corresponding compounds of formula IV:
Figure imgf000010_0002
*2 • where R is as defined hereinbefore, either with methyl formate in the presence of a base, and then with dimethyl sulfate in the presence of a base, to give the desired compounds where X is CH, or with an alkyl nitrite in the presence of a base, and then with dimethyl sulfate in the presence of a base, to give the desired compounds where X is N.
The compounds of formula I in which A is 0 and X is N can be prepared in two steps from compounds of formula I where A is O and X is CH by ozonolysis followed by treatment of the resulting keto ester with methoxylamine hydrochloride.
The compounds of formula I in which A is NH and X is N may be prepared from the corresponding compounds of formula I in which A is 0 and X is N by reaction thereof with methylamine in a suitable solvent, e.g. methanol, to give the desired compounds. The compounds of formula I in which A is NH and X is CH may be prepared from the corresponding compounds of formula I in which A is 0 and X is CH by converting the -C02CH3 group to -C02H by means of lithium iodide in a suitable solvent medium, e.g. dimethylformamide, followed by chlorination using thionyl chloride, and reaction of the compound so formed with methylamine by methods known per se to give the desired compound.
Other methods will be apparent to the chemist skilled in the art as will be the methods for preparing starting materials and intermediates. The Examples also make apparent va'rious methods of preparing compounds of the invention as well as starting materials and intermediates.
The invention is illustrated in the following Examples. Structures of isolated novel compounds were confirmed by appropriate analyses, e.g. 1 H nmr, mass spectrometry and IR spectroscopy.
Example 1
Methyl (E)-3-methoxy-2-f7-f 1 -(2-pyridyl)ethylideneaminooxymethyll-1 -naphthyl1 acrylate (Compound 1 ) A solution of methyl (E)-2-(7-bromomethyl-1 -naphthyl)-3-methoxyacrylate ( 1 g), 2-acetylpyridine oxime (0.41 g) and tetrabutylammonium hydrogen sulfate ( 1 .32 g) in dichloromethane (3 ml) and 2M sodium hydroxide (3 ml) was vigorously stirred for 4 hours at room temperature. The solution was diluted with water (25 ml), the dichloromethane layer separated and the aqueous solution extracted with dichloromethane (25 ml). The organic extracts were combined, dried (MgS04) and concentrated in vacuo. The residue was purified by silica gel chromatography to obtain the title product as a single geometric isomer of the oxime, m.p. 1 07-109 °C (Compound 1 ).
Preparation of startinσ materials a) Methyl 7-methyl-1 -naphthylacetate
A solution of 7-methyl-1 -naphthylacetic acid ( 1 6.3 g) and concentrated sulfuric acid (2 ml) in methanol (300 ml) was heated at reflux for 7 hours. The solution was cooled to room temperature, water (500 ml) was added and the mixture was extracted with ether (4x250 ml). The organic extracts were washed with saturated aqueous sodium bicarbonate (250 ml) and water ( 1 00 ml), and dried (MgS0 ). Evaporation in vacuo gave the title compound which was used without purification.
b) Methyl (E)-3-methoxy-2-(7-methyl-1 -naphthvDacrylate
A solution of methyl 7-methyl-1 -naphthylacetate (1 1 .3g) and methyl formate (25.3 g) was added dropwise at 5 °C to a suspension of sodium methoxide (5.7 g) in toluene ( 100 ml). The mixture was stirred at 5 °C for 1 .5 hours and then at room temperature for 3 hours before pouring onto a solution of ice/water (300 ml) and concentrated ydrochloric acid (1 5 ml). The organic extract was separated, concentrated in vacuo and the residue dissolved in toluene ( 100 ml). The resulting solution was added dropwise at 10 ° C to a suspension of sodium methoxide (3.1 g) in toluene (100 ml) and stirred at 10 °C for 30 minutes. Dimethyl sulfate (9.9g) in toluene (10 ml) was then added and stirring was continued for 1 8 hours. Water ( 100 ml) was added, the layers were separated and the aqueous layer was extracted with toluene (100 ml). Concentrated sulfuric acid (5 drops) was added to the combined organic extracts and the mixture was heated at reflux for 2 hours. The reaction mixture was cooled, washed with saturated aqueous sodium bicarbonate (100 ml), dried (MgS0 ), and concentrated in vacuo. The residue was triturated with petroleum ether (60-80)/diisopropyl ether (40 ml) to give the title product, m.p. 1 1 7-1 1 9°C.
c) Methyl (E)-2-(7-bromomethyl-1 -naphthyl)-3-methoxyacrylate A solution of methyl (E)-3-methoxy-2-(7-methyl-1 -naphthyl)acrylate (2.6 g) and N- bromosuccinimide (1 .9 g) in carbon tetrachloride ( 1 00 ml) was heated at reflux for 2 hours under UV light. After cooling, the solid was filtered and the filtrate was concentrated in vacuo. The residue was purified by silica gel chromatography followed by trituration with diisopropyl ether to give the title product, m.p. 98- 101 °C.
In a similar manner the following compounds of formula I , where R2 is H, X is CH, A is 0 and the substituent R3R4C = N-0-CHR2 is in the 7-position of the naphthalene ring, were prepared by methods analogous to those of Example 1 . Cmpd R3 R4 m.p.
2 Me Me 103-105
3 Ph Me 120-122
4 Me H 79-85
5 2-MePh H 112-114
6 MeCO Me 106-108
7 -(CH2)4- 118-120
8 CONHMe CN 141-143
9 CONMe2 CN 65-70
10 4,6-diMeO-2- CN 157-160 pyrimidinyl
11 2-CIPh H 103-105
12 2-MePh Me 95-97
13 3-pyridyl H 144-146
14 2-N02Ph H 105-109
15 4-CIPh H 170-171
16 4-pyridyl H 143-145
17 2-pyridyl H 133-135
18 Ph H 132-134
19 2-MeOPh H 124-126
20 Bu1 Me 83-85
21 3-MePh H 109-111
22 4-MePh H 145-147
23 2-thienyl Me 116-118
24 3-pyπdyl Me 100-102 Cmpd R3 R4 m.p.
25 4-pyridyl Me 163-165
26 2-pyridyl 2-pyridyl 161-163
27 2-furyl Me 115-116
28 2-pyridyl Bu1 111-112
29 2-pyridyl CN 152-154
3O 2-pyridyl Ph 105-106
31 Ph 2-pyridyl 145-147
32 2-pyridyl-C( = 0)- 2-pyridyl 167-170
33 2-pyridyl Et 123-124
34 2-pyrazinyl Me 111-112
35 Ph CF3 116-118
36 N-methyl-2-pyrrolyl Me 147-149
37 2-pyridyl Pr1 120-122
38 Pr1 2-pyridyl 113-115
39 2-pyridyl C02Et 109-110
40 PhC( = NOMe)- Me 147-148
41 MeC( = NOMe)- Me 102-104
42 4-pyrimidinyl H 130-132
43 4,6-diMe-2- Me 124-127 pyrimidinyl
44 2-pyrimidinyl Me 157-159
All compounds 1-44 were assigned as the E geometry about the acrylate double bond. All compounds, except for 30, 31, 37 and 38, were isolated from the reaction as a single isomer about the oxime C = N bond. Compounds 30 and 31, and 37 and 38 , were isolated as two isomers, isomeric about the oxime C = N bond.
Example 2 Isomerisation of the oximino group in Compound 1
A solution of Compound 1 (300 mg) in acetone (8 ml) was placed in a Petri dish and the solvent allowed to evaporate. The resulting thin film was photolysed with UV radiation for 14 hours and then purified by silica gel chromatography to give the isomeric oxime of Compound 1 , m.p. 1 28-1 30°C (Compound 45).
Example 3
Methyl 2-(E and Z)-methoxyimino-2-{7-π -(2-pyridyl)ethylideneaminooxymethyll-1 - naphthyljacetate
A solution of methyl 2-{7-[ 1 -(2-pyridyl)ethylideneaminooxymethyll-1 -naphthyl}-2- oxoacetate (0.91 g) and methoxylamine hydrochloride (0.42 g) in methanol (50 ml) was heated under reflux for 2 hours. The solution was cooled to room temperature, concentrated in vacuo, and the residue partitioned between diethyl ether (25 ml) and aqueous saturated sodium bicarbonate solution (25 ml). The aqueous phase was extracted with ethyl acetate (2 x 25 ml), and all organic phases were combined. The combined organic phases were washed with water ( 1 0 ml), dried (MgS0 ), concentrated in vacuo, and purified by silica gel chromatography to give the title compounds as two separable isomeric oximes, m.p. 79-81 °C (Example 46) and m.p. 1 07-109 °C (Example 47)
Preparation of starting material
Methyl 2-{7-π -(2-pyridyl)ethylideneaminooxymethyl1-1 -naphthyl}-2-oxoacetate Ozone was bubbled into a solution of Compound 1 ( 1 g) in dichloromethane (50 ml) at -78 °C for 10 minutes. The solution was purged with nitrogen for 10 minutes, dimethyl sulfide ( 1 ml) added, and the solution allowed to warm to room temperature. The solution was stirred for 1 8 hrs and the solvent removed to give the title compound. Example 4
Methyl 2-methoxyimino-Λ/-methyl-2-(7-f 1 -(2-pyridyl)ethylideneaminooxymethvH-1 - naphthyl}acetamide
A solution of methanolic methylamine (5 ml, 22% w/v) and Compound 46 (160 mg) was stirred at room temperature for 18 hours. The solution was then concentrated in vacuo and the residue triturated with diisopropyl ether (5 ml) to give the title compound, m.p. 1 56-1 58 °C (Compound 48).
In analogous fashion to Example 3, Compound 47 was converted to the methoxyimino isomer of Compound 48, m.p. 167-168 °C (Compound 49).
In a similar manner to one of the previous Examples, the following compounds of formula I, where R2 is H, R3 is 2-pyridyl and R4 is methyl could aiso be prepared b methods analogous to those of the previous Examples. The column headed
"Position" is the position of the substituent R3R4C = N-0-CHR2 on the naphthalene ring,
Cmpd Position X A. m.p.
49 5 CH 0
50 6 CH 0
51 8 CH 0
52 5 N 0
53 6 N 0
54 8 N 0
55 5 N NH
56 6 N NH
57 8 N NH
58 7 CH NH
Test Example Compounds are assessed for activity against one or more of the following: Phytophthora infestans: late tomato blight Plasmopara viticola: vine downy mildew Erysiphe graminis f. sp. hordei: barley powdery mildew Erysiphe graminis f. sp. tritici: wheat powdery mildew Pyricularia oryzae: rice blast
Pellicularia sasakii: rice sheath blight
Botrytis cinerea: grey mould
Venturia inaequalis: apple scab Leptosphaeria nodorum: glume blotch
Aqueous solutions or dispersions of the compounds at the desired concentration, including a wetting agent, were applied by spray or by drenching the stem base of the test plants, as appropriate. Plants or plant parts were then inoculated with appropriate test pathogens and kept under controlled environment conditions suitable for maintaining plant growth and development of the disease. After an appropriate time, the degree of infection of the affected part of the plant was visually estimated. Compounds were considered active if they gave greater than 50% control of the disease at a concentration of 500 ppm (w/v) or less.
Compounds 2-5, 7 and 1 8 showed activity against Phytophthora infestans;
Compounds 4, 5, 1 3, 1 6- 1 9 and 22 showed activity against Plasmopara viticola;
Compounds 1 , 3-5, 7, 1 1 , 1 2, 14-20, 24 and 27-29 showed activity against
Erysiphe graminis f sp. hordei;
Compounds 1 , 3-5, 7, 1 2-1 7, 21 , 22 and 37 showed activity against Pyricularia oryzae;
Compounds 1 , 3-5, 9, 1 1 -22, 25 , 29, 37, 38 and 40 showed activity against
Pellicularia sasakii;
Compound 5 showed activity against Botrytis cinerea;
Compound 1 -5 showed activity against Venturia inaequalis; Compounds 5, 1 1 , 1 3, 1 4, 1 7, 1 8 , 21 -23, 28 and 29 showed activity against
Leptosphaeria nodorum; and.
Compounds 21 and 23 showed activity against Erysiphe graminis f. sp. tritici

Claims

1 ) Compounds of formula
Figure imgf000018_0001
where:
A is NH or 0;
X is N or CH;
R2 is hydrogen or alkyl;
R3 and R4, which may be the same or different, are alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkoxy, alkylthio, phenyl or heterocyclyl, each of which is optionally substituted, hydrogen, cyano, a group - COR20 or a group -C(R21) = N-OR22, with the proviso that R3 and R4 are not simultaneously hydrogen; or
R3 and R4, together with the carbon atom to which they are attached, form an optionally substituted 5- to 7-membered ring optionally including one to three heteroatoms selected from N, 0 and S;
20
R is alkyl, cycloalkyl, phenyl, heterocyclyl or amino, each of which is optionally substituted, or is hydrogen; 1 20
R has the same meaning as R and may also be cyano; and
22 20 20
R has the same meaning as R and may also be -COR .
Compounds according to claim 1 wherein the substituent
R3R4C = N-0-CHR2 is attached to the 7 position of the naphthalene ring system.
Compounds according to claim 1 or 2 wherein R is hydrogen.
Compounds according to any one of the preceding claims wherein X is CH and A is 0 or X Is N and A is 0 or NH. Compounds according to any one of the preceding claims wherein R3 is heteroaryl.
Compounds according to claim 5 wherein R3 is a nitrogen containing heteroaryl of 5 or 6 carbon atoms
3 Compounds according to claim 6 wherein R is pyridyl.
, Compounds according to any one of the preceding claims wherein R is hydrogen or alkyl.
A fungicidal composition comprising compounds as claimed in any one of the preceding claims in admixture with an agriculturally acceptable diluent or carrier.
PCT/GB1996/001948 1995-08-16 1996-08-09 Alpha-methoxymethylene or alpha-methoxyimino naphthylacetic acid derivatives and their use as fungicides Ceased WO1997007099A1 (en)

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