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GB2305173A - N-(heterocyclylmethylene)-2-(carboxy or heterocyclyl)aniline derivatives as fungicides - Google Patents

N-(heterocyclylmethylene)-2-(carboxy or heterocyclyl)aniline derivatives as fungicides Download PDF

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Publication number
GB2305173A
GB2305173A GB9618457A GB9618457A GB2305173A GB 2305173 A GB2305173 A GB 2305173A GB 9618457 A GB9618457 A GB 9618457A GB 9618457 A GB9618457 A GB 9618457A GB 2305173 A GB2305173 A GB 2305173A
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optionally substituted
heterocyclyl
group
cycloalkenyl
cycloalkyl
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GB9618457D0 (en
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Brian Anthony Moloney
Peter John West
Peter Dominic Riordan
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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
    • 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
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/40—Acylated substituent nitrogen atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/56—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having carbon atoms of carboxamide groups bound to carbon atoms of carboxyl groups, e.g. oxamides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/81—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
    • 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
    • C07D213/60—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
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • 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
    • C07D213/60—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
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/69—Two or more oxygen 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
    • C07D213/60—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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
    • 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
    • C07D333/26—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 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
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

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

Abstract

Compounds of formula I: [where:A is an optionally substituted 5- or 6-membered heterocyclic ring which comprises at least one hetero atom (selected from nitrogen, sulfur and oxygen and is optionally fused); R 1 is an optionally substituted alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl or amino group, Y-X-, halogen, cyano, nitro, acyl, heterocyclyl or aryl; or two adjacent groups together with the carbon atoms to which they are attached can form an optionally substituted benzo ring; Z is C( =X 1 )-X 2 -R 3 , or a group as defined above for A; R 3 is hydrogen or an optionally substituted alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, heterocyclyl or aryl group; Y is hydrogen, acyl or an optionally substituted alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, aryl or heterocyclyl group; X, X 1 and X 2 , which may be the same or different, are O or S; W is halogen, cyano, or a group -OR or -SR, where R is an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl or acyl group; and n is 0 to 4] and salts and complexes thereof, have use as plant fungicides.

Description

Case 95C114 This invention relates to new derivatives of anthranilic acid useful as fungicides.
In GB 1,563,664 and Japanese Kokai 53130655 and 53072825, there are disclosed fungicidal esters of anthranilic acid. We have found that certain novel anthranilic acid derivatives also have valuable fungicidal activity and also have advantages over compounds disclosed in these publications.
In one aspect the invention provides the compounds of formula I:
where: A is an optionally substituted 5- or 6-membered heterocyclic ring which comprises at least one hetero atom selected from nitrogen, sulfur and oxygen; R' is an optionally substituted alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl or amino group, Y-X-, halogen, cyano, nitro, acyl, heterocyclyl or aryl; or two adjacent groups together with the carbon atoms to which they are attached can form an optionally substituted benzo ring; Z is C(=X1)-X2-R3 or a group as defined above for A; R is hydrogen or an optionally substituted alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, heterocyclyl or aryl group; Y is hydrogen, acyl or an optionally substituted alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, aryl or heterocyclyl group; X, Xr and X2, which may be the same or different, are 0 or S; W is halogen, cyano, or a group -OR or -SR, where R is an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl or acyl group; and n is O to 4.
together with complexes with metal salts, as well as salts with bases of compounds which are acids and salts with acids of compounds which are bases.
When ring A is substituted, possible substituents include those defined above for under R1 or two adjacent groups together with the carbon atoms to which they are attached form an optionally substituted heterocyclic ring; Alkyl groups are preferably of 1 to 20, eg 1 to 6, carbon atoms. Alkenyl and alkynyl groups are generally of 3 to 6 carbon atoms. Cycloalkyl or cycloalkenyl groups are preferably of 3 to 8 carbon atoms.
Substituents, when present on any alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, alkoxy or alkylthio group, may include halogen, cyano, alkoxy (eg of 1 to 4 carbon atoms, and which may be substituted, eg by halo), hydroxy, alkyithio, nitro, optionally substituted amino, carboxy, alkoxycarbonyl, acyl, acyloxy, heterocyclyl and aryl.
Cycloalkyl or cycloalkenyl groups may also be substituted by alkyl.
Aryi groups are usually phenyl, optionally substituted, eg by one or more of the same groups as defined for R'.
The term heterocyclyl includes both aromatic and non-aromatic heterocyclyl groups. Heterocyclyl groups are generally 5 or 6-membered rings containing up to 3 hetero atoms from nitrogen, oxygen and sulfur. The heterocyclyl groups may be fused to a benzene ring to form a fused heterocyclyl group. Examples of heterocyclyl groups are thienyl, furyl, pyridyl, pyrimidinyl, pyrazolyl, thiazolyl, thiazolinyl, oxazolyl, benzimidazolyl, tetrazolyl, benzoxazolyl, thiadiazolyl, oxadiazolyl, dioxolanyl, imidazopyridinyl, 1 ,3-benzoxazinyl, 1,3-benzothiazinyl, oxazolopyridinyl, triazolyl, triazinyl, imidazolyl, morpholino, benzofuranyl, pyrazolinyl, quinolinyl, quinazolinyl, sulfolanyl, dihydroquinazolinyl, benzothiazolyl, piperidinyl, phthalimido, 2-oxopyrrolidino, 2-oxobenzoxazolin-3-yl.
and benzofuranyl. Heterocyclyl groups may themselves be substituted for example as for phenyl.
Amino groups may be substituted for example by one or two optionally substituted alkyl or acyl groups, or two substituents can form a ring, preferably a 5 to 7-membered ring, which may be substituted and may contain other hetero atoms, for example morpholine, thiomorpholine, or piperidine.
The term acyl includes the residue of sulfur and phosphorus-containing acids as well as carboxylic acids. Examples of acyl groups are thus -CoR5, -COOR5, -CXNR 5R6, -CoN(R5)0R6, -COONR 5R6, -CoN(R5)NR6R7, -COSRS, -CSSR5, -s(o)pR5, -S(0)20R5, -S(o)pNR5R6, -P(=X)(0R5)(OR6), -CO-COOR5, 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, aryl or 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 X is O or S.
Complexes of compounds of the invention are usually formed from a salt of formula MAn2, in which M is a divalent metal cation, eg copper, manganese, cobalt, nickel, iron or zinc and An is an anion, eg chloride, nitrate or sulfate.
The compounds of the invention have activity against a wide range of pathogens of Deuteromycete, Ascomycete, Phycomycete and Basidiomycete origin, and especially against fungal diseases of plants, eg mildews and particularly cereal powdery mildew (Erysiphe graminis) and vine downy mildew (Plasmopara viticola), rice blast (Pyricularia oryzae), rice sheath blight (Pel/icularia sasakii), apple scab (Venturia inaequalis), glume blotch (Leptosphaeria nodorum), late blight (Phytophthora in fes tans), and grey mould (Botrytis cinerea).
The compounds of the invention are generally formulated in conventional compositions used for fungicides. These compositions can contain one or more additional pesticides, for example compounds known to possess herbicidal, fungicidal, insecticidal, acaricidal or nematicidal properties.
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 al kylphenol sulfates; lignin sulfonates; petroleum sulfonates; alkyl-aryl sulfonates such as alkyl-benzene sulfonates or lower alkylnaphthalene sulfonates, eg butyl-naphthalene sulfonate; salts of sulfonated naphthalene-formaldehyde condensates; salts of sulfonated phenol-formaldehyde condensates; or more complex sulfonates such as the amide sulfonates, eg the sulfonated condensation product of oleic acid and N-methyl taurine or the dialkyl sulfosuccinates, eg the sodium sulfonate of dioctyl succinate. Nonionic agents include condensation products of fatty acid esters, fatty alcohols, fatty acid am ides or fatty-alkyl- or alkenyl-substituted phenols with ethylene oxide, fatty esters of polyhydric alcohol ethers, eg sorbitan fatty acid esters, condensation products of such esters with ethylene oxide, eg 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 aiiphatic 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.
As a dispersion, the composition comprises a compound of the invention dispersed in a liquid medium, preferably water. It is often convenient to supply the consumer with a primary composition which can be diluted with water to form a dispersion having the desired concentration. The primary composition can be provided in any one of the following forms. It can be a dispersible solution which comprises a compound of the invention dissolved in a water-miscible solvent with the addition of a dispersing agent. A further alternative comprises a compound of the invention in the form of a finely ground powder in association with a dispersing agent and intimately mixed with water to give a paste or cream which can if desired be added to an emulsion of oil in water to give a dispersion of active ingredient in an aqueous oil emulsion.
An emulsifiable concentrate comprises a compound of the invention dissolved in a water-immiscible solvent together with an emulsifying agent and which is formed into an emulsion on mixing with water.
A dusting powder comprises a compound of the invention intimately mixed 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 adsorbed or absorbed on a pre-granular diluent, for example, Fuller's earth, attapulgite or limestone grit.
A wettable powder usually comprises the active ingredient in admixture with a suitable surfactant and an inert powder diluent such as china clay.
Another suitable concentrate, particularly when the product is a solid, is a flowable suspension concentrate which is formed by grinding the compound with water, a wetting agent and a suspending agent.
The concentration of the active ingredient in the composition of the present invention is preferably within the range of 1 to 30 per cent by weight, especially 5 to 30 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.
The compounds of formula I where W is halogen may be prepared by reacting a compound of formula:ll
where A, Z, R1 and n are as defined hereinbefore with a thionyl halide SOHal2 to give the desired compound.
The compounds of formula ll may be prepared by methods analogous to those described in our international Application No PCT/GB95/00570, for example by reacting a compound of formula:lll
where Z, R1 and n are as defined hereinbefore, with a compound of the formula:
where Q is a leaving group, preferably a halogen and especially chlorine, and A is as defined hereinbefore, to give the desired compound.
The reaction between compounds Ill and IV is generally carried out in the presence of a base, eg an organic tertiary amine and preferably in the presence of a solvent, eg an ether.
The compounds of formula Ill and IV are either known or can be prepared in known manner.
The compounds of formula I where W is cyano or a group -OR or -SR may be prepared from the corresponding compounds of formula I in which W is halogen by methods known per se, for example as described in European Patent No 8145.
Alternatively, the compounds of formula I where W is a group SR may be prepared by reacting a compound of formula Il as defined hereinbefore with Lawesson's reagent to give the corresponding compound in which the =0 group is replaced by =S, and the compound so produced is then reacted in the presence of a base with an appropriate halide RHal where R is as defined hereinbefore to give the desired compound.
The invention is illustrated in the following Examples. Structures of isolated novel compounds were confirmed by elemental and/or other appropriate analyses.
Temperatures are in "C.
ExamDle 1 Methvl N-r(6-methoxv-3-Dvridvl ) (methvlthio)methvlene l-anthranilate (a) Methvl N-86-methoxvDvridine-3-carbothiovl)-anthranilate Methyl N-(6-methoxynicotinoyl)anthranilate (1.439), prepared according to the methods described in PCT/GB95/00570, Lawesson's reagent (2,4-bis(4 methoxyphenyl)-1 ,3-dithia-2,4-diphosphetane 2,4-disulfide, 3.049) and dry tetrahydrofuran (50ml) were refluxed with stirring for 1 8 hours, after which the mixture was poured into brine and extracted with ether. It was then washed with water, dried over magnesium sulfate and evaporated down.The residue was chromatographed on silica (259) using 2:1 dichloromethane/petrol as eluent, followed by dichloromethane, to give the desired product as a yellow solid, mp 133-134".
(b) Methvl N-i(6-methoxv-3-ovridvl ) (methvlthiol-methvleneianthranilate The product of stage (a) (370mg), potassium carbonate (170mg) and dry dimethylformamide (Sml) were stirred at room temperature for 1 hour, then methyl iodide (174mg) was added, and the mixture was stirred for 2 hours. The reaction mixture was then poured into water and extracted with diethyl ether, the combined extracts being dried over magnesium sulfate and evaporated down. The residue was chromatographed on silica (209) using 3:1 petrol/diethyl ether to give the desired product as a green oil.
Further ExamDles The following compounds of formula I may be prepared by methods analogous to that of Example 1: A W (R1)n z 6-MeO-3-pyridyl CN - COO Me 6-MeO-3-pyridyl OMe - COOMe 6-MeO-3-pyridyl SPh - COOMe 5-CI,6-MeO-3-pyridyl SMe - COO Me 2-MeO-5-pyrimidinyl SMe - COO Me 5-CI-2-thienyl SMe - COO Me 6-MeO-3-pyridyl SMe - oxazol-2-yl 6-MeO-3-pyridyl SMe - COOEt 6-MeO-3-pyridyl SMe CO2CH2CH = CH2 6-MeO-3-pyridyl SMe - 1 ,3,4-thiadiazol-2-yl 6-MeO-3-pyridyl SMe 4-COOMe COOMe 6-MeO-3-pyridyl SMe 4,5-di(OMe) COOMe 6-MeO-3-pyridyl SMe 4-CI COOMe 6-MeO-3-pyridyl SMe 5-Me COO Me 6-MeO-3-pyridyl SMe 4-F COO Me 6-MeO-3-pyridyl CN - oxazol-2-yl 6-MeO-3-pyridyl OMe - 1 ,2,4-oxadiazol-2-yl 2-MeO-5-pyrimidinyl OMe - COOMe 5-Br-2-furyl Ph - COOMe A W (R)n Z 6-MeO-3-pyridyl S-tBu 4-F COO Me 6-MeO-3-pyridyl OPh 5-Me COO Me 2-CI-4-pyridyl SMe - COOEt 5-CI-6-MeO-3-pyridyl SMe 4-F COO Me 6-MeO-3-pyridyl SMe 4-F COOEt 2-MeO-4-pyridyl OMe 1 ,2,4-oxadiazol-2-yl 2,6-diCI-4-pyridyl S(2-pyridyl) 5-Me COO Me 6-MeO-3-pyridyl SCH2Ph 4-CI CO2CH2CH=CH2 5-CI-3-thienyl SMe 4-F CO2CH2CH20Me 5-CI-6-MeO-3-pyridyl S(4-CIPh) 4-CI COOiPr Test ExamDle Compounds are assessed for activity against one or more of the following: Phytophthora in fes tans: late blight (Pl) Plasmopara viticola: vine downy mildew (PV) Erysiphe graminis: powdery mildew (EG) Pyricularia oryzae: rice blast (PO) Pellicularia sasakii: rice sheath blight (PS) Venturia inaequalis: apple scab (Vl) Botrytis cinerea: grey mould (BC) Leptosphaeria nodorum: glume blotch (LN) 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 1 showed activity against Erysiphe graminis.

Claims (1)

1. The compounds of formula I:
where: A is an optionally substituted 5- or 6-membered heterocyclic ring which comprises at least one hetero atom selected from nitrogen, sulfur and oxygen; R1 is an optionally substituted alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl or amino group, Y-X-, halogen, cyano, nitro, acyl, heterocyclyl or aryl; or two adjacent groups together with the carbon atoms to which they are attached can form an optionally substituted benzo ring; Z is C(=X1)-X2-R3, or a group as defined above for A; R is hydrogen or an optionally substituted alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, heterocyclyl or aryl group; Y is hydrogen, acyl or an optionally substituted alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, aryl or heterocyclyl group; X, X1 and X2, which may be the same or different, are 0 or S; W is halogen, cyano, or a group -OR or -SR, where R is an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl or acyl group; and n is O to 4.
together with complexes with metal salts, as well as salts with bases of compounds which are acids and salts with acids of compounds which are bases.:
GB9618457A 1995-09-16 1996-09-04 N-(heterocyclylmethylene)-2-(carboxy or heterocyclyl)aniline derivatives as fungicides Withdrawn GB2305173A (en)

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Publication number Priority date Publication date Assignee Title
US8158828B2 (en) 2005-11-28 2012-04-17 Gtx, Inc. Nuclear receptor binding agents
US8546451B2 (en) 2005-11-28 2013-10-01 Gtx, Inc. Estrogen receptor ligands and methods of use thereof
US8637706B2 (en) 2005-11-28 2014-01-28 Gtx, Inc. Nuclear receptor binding agents
US9051267B2 (en) 2005-11-28 2015-06-09 Gtx, Inc. Estrogen receptor ligands and methods of use thereof
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US9427418B2 (en) 2009-02-23 2016-08-30 Gtx, Inc. Estrogen receptor ligands and methods of use thereof
US9624161B2 (en) 2009-02-23 2017-04-18 Gtx, Inc. Estrogen receptor ligands and methods of use thereof

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GB2305177A (en) 1997-04-02

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