GB2238308A - Methyl 2-substituted-3-methoxy-2-propenoates as fungicides - Google Patents

Methyl 2-substituted-3-methoxy-2-propenoates as fungicides Download PDF

Info

Publication number
GB2238308A
GB2238308A GB9023018A GB9023018A GB2238308A GB 2238308 A GB2238308 A GB 2238308A GB 9023018 A GB9023018 A GB 9023018A GB 9023018 A GB9023018 A GB 9023018A GB 2238308 A GB2238308 A GB 2238308A
Authority
GB
United Kingdom
Prior art keywords
optionally substituted
compounds
alkyl
formula
plants
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
GB9023018A
Other versions
GB9023018D0 (en
Inventor
John Martin Clough
Christopher Richard Ay Godfrey
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Imperial Chemical Industries Ltd
Original Assignee
Imperial Chemical Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Publication of GB9023018D0 publication Critical patent/GB9023018D0/en
Publication of GB2238308A publication Critical patent/GB2238308A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
    • A01N43/70—Diamino—1,3,5—triazines with only one oxygen, sulfur or halogen atom or only one cyano, thiocyano (—SCN), cyanato (—OCN) or azido (—N3) group directly attached to a ring carbon atom
    • 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
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D237/20—Nitrogen atoms
    • 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
    • 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
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/34—One oxygen atom
    • 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
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/38—One sulfur atom
    • 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
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One nitrogen atom
    • 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
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/18—Oxygen or sulfur atoms
    • 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
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/20—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
    • C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
    • C07D253/06—1,2,4-Triazines
    • C07D253/065—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members
    • C07D253/07—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members with hetero atoms, or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Compounds having the formula (I): <IMAGE> [wherein X is a 6-membered aromatic carbon-nitrogen heterocycle containing 1 to 3 nitrogen atoms and linked to Y, Z and Z<1> by any of its carbon atoms, or a N-oxide derivative thereof; Y is O, s, CR<1>R<2> or NR<3> (wherein R<1>, R<2> and R<3> are independently H or C1-4 alkyl); Z is one of a wide range of specified substituents, but preferably optionally substituted aryl or heteroaryl; n is 0, 1, 2 or 3; Z<1> is a specified single atom or a sterically small group; and, when n is 2 or 3, the values of Z<1> may be the same or different] are useful as plant fungicides.

Description

FUNGICIDES This invention relates to derivatives of propenoic acid useful as fungicides, to processes for preparing them, to fungicidal compositions containing them, and to methods of using them to combat fungi, especially fungal infections of plants.
According to the invention there are provided compounds having the formula (I):
and stereoisomers thereof, wherein X is a 6-membered aromatic carbon-nitrogen heterocycle containing 1 to 3 nitrogen atoms and linked to Y, Z and zl by any of its carbon atoms, or a N-oxide derivative thereof;Y is 0, S, CR1R2 or NR3, wherein R1, R2 and R3 are independently H or C14 alkyl; z is H, halo, hydroxy, optionally substituted alkoxy, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylthio, optionally substituted heteroaryl, optionally substituted heteroaryloxy, optionally substituted heteroarylthio, optionally substituted acyloxy, optionally substituted amino, optionally substituted arylazo, optionally substituted acylamino, nitro, cyano, -CO2R4, -CONR4R5, -COR4, -CR4-NR5, -N-CR4R5 or -S(O)mR4, wherein m is 0, 1 or 2; and R4 and R5, which are the same or different, are H, alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl or optionally substituted aryl; zl is halo, hydroxy, methyl, halomethyl, methoxy, halomethoxy, cyano, nitro, amino, methylamino or dimethylamino; n is 0, 1, 2 or 3; and, when n is 2 or 3, the values of zl may be the same or different.
The compounds of the invention contain at least one carbon-carbon double bond, and are sometimes obtained in the form of mixtures of geometric isomers. However, these mixtures can be separated into individual isomers, and this invention embraces such isomers, and mixtures thereof in all proportions including those which consist substantially of the (Z)-isomer and those which consist substantially of the (E)-isomer.
The individual isomers which result from the unsymmetrically substituted double bond of the propenoate group are identified by the commonly used terms "E" and "z". These terms are defined according to the Cahn Ingold-Prelog system which is fully described in the literature (see, for example, J March, "Advanced Organic Chemistry", 3rd edition, Wiley-Interscience, page 109 et seq).
Usually one isomer is more active fungicidally than the other, the more active isomer usually being the one wherein the groups -CO2CH3 and -OCH3 are on opposite sides of the olefinic bond of the propenoate group. In the case where Y is O, S or NR3, this is the (Z)-isomer. In the case where Y is CR1R2, it is the (~)-isomer.
In the compounds of formula (I), halo includes fluoro, chloro, bromo, and iodo. Alkyl groups and the alkyl moiety of alkoxy groups can be in the form of straight or branched chains, and preferably contain 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.
Examples are methyl, ethyl, propyl (n- and iso-propyl) and butyl (n-, sec-, iso- and tert-butyl). Cycloalkyl groups include cyclohexyl and cycloalkylalkyl groups include cyclopropylethyl. Alkenyl and alkynyl groups preferably contain 2 to 6, more preferably 2 to 4, carbon atoms in the form of straight or branched chains. Examples are ethenyl, allyl and propargyl.Optionally substituted alkyl includes, in particular, haloalkyl, hydroxyalkyl, alkoxyalkyl, optionally substituted aralkyl (for example, optionally substituted benzyl, phenethyl or phenyl n-propyl), optionally substituted aryloxyalkyl (for example, optionally substituted phenoxyalkyl), optionally substituted heteroarylalkyl and optionally substituted heteroaryloxyalkyl; optionally substituted alkoxy includes haloalkoxy, hydroxyalkoxy, alkoxyalkoxy, optionally substituted arylalkoxy (for example, benzyloxy), optionally substituted aryloxyalkoxy, optionally substituted heteroarylalkoxy and optionally substituted heteroaryloxyalkoxy; optionally substituted alkenyl includes optionally substituted phenylalkenyl (for example, optionally substituted phenylethenyl); and optionally substituted alkynyl includes optionally substituted phenylalkynyl.
The acyl moiety of acyloxy and acylamino includes carbacyl (for example, benzoyl and C14 alkanoyl).
Optionally substituted amino includes NR'R" in which R' and R" are as hereinafter defined.
Aryl groups, including the aryl moieties of, for example, aryloxy and aralkyl, include phenyl in particular, and naphthyl. Heteroaryl groups, including the heteroaryl moieties of, for example, heteroaryloxy and heteroarylalkyl, include 5- and 6-membered heteroaryl groups containing one or more of each of the heteroatoms O, S and N (preferably S or N), fused benzenoid and heteroaromatic ring systems, and, in each case, the corresponding N-oxides. Examples of heteroaryl groups are pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, 1,2,3, 1,2,4-, and 1,3,5-triazinyl, 1,2,4,5-tetrazinyl, 1,2,3and 1,2,4-triazolyl, thienyl, furyl, pyrrolyl, thiazolyl, oxadiazolyl, quinolinyl, isoquinolinyl, quinoxalinyl, benzothienyl, benzoxazolyl and benzthiazolyl and, where appropriate, the corresponding N-oxides.
Where valency allows, optionally substituted aryl and heteroaryl groups can carry up to 5 substitutents.
Substituents which may be present include one or more of the following; halo, hydroxy, mercapto, C1-4 alkyl (especially methyl and ethyl), C2-4 alkenyl (especially allyl), C2-4 alkynyl (especially propargyl), C1-4 alkoxy (especially methoxy), C2-4 alkenyloxy (especially allyloxy), C24 alkynyloxy (especially propargyloxy), halo(C1 4)alkyl (especially trifluoromethyl), halo(C1 4)alkoxy (especially trifluoromethoxy), C1-4 alkylthio (especially methylthio), hydroxy(C1-4)alkyl, C14 alkoxy(C14)alkyl, C36 cycloalkyl, C3~6 cycloalkyl(C1 4)alkyl, optionally substituted aryl (especially optionally substituted phenyl), optionally substituted heteroaryl (especially optionally substituted pyridinyl or pyrimidinyl), optionally substituted aryloxy (especially optionally substituted phenoxy), optionally substituted heteroaryloxy (especially optionally substituted pyridinyloxy or pyrimidinyloxy), optionally substituted aryl(C1 4)alkyl (especially optionally substituted benzyl, optionally substituted phenethyl and optionally substituted phenyl n-propyl) in which the alkyl moiety is optionally substituted with hydroxy, optionally substituted heteroaryl(C1 4)alkyl (especially optionally substituted pyridinyl- or pyrimidinyl(C1 4)alkyl), optionally substituted aryl(C2 4)alkenyl (especially optionally substituted phenylethenyl), optionally substituted heteroaryl(C2 4)alkenyl (especially optionally substituted pyridinylethenyl or pyrimidinylethenyl), optionally substituted aryl(C1 4)alkoxy (especially optionally substituted benzyloxy), optionally substituted heteroaryl(C1 4)alkoxy (especially optionally substituted pyridinyl- or pyrimidinyl(C1 4)alkoxy), optionally substituted aryloxy(C1-4)alkyl (especially phenoxymethyl), optionally substituted heteroaryloxy(C1 4)alkyl (especially optionally substituted pyridinyloxy- or pyrimidinyloxy(C1-4)alkyl), acyloxy, including C1-4 alkanoyloxy (especially acetyloxy) and benzoyloxy, cyano, thiocyanato, nitro, -NR'R", -NHCOR', -NHCONR'R", -CONR'R", -COOR', -OSO2R', -SO2R', -COR', -CR'-NR" OR -N-CR R in which R and R" are independently hydrogen, C1-4 alkyl, C1-4 alkoxy, C1-4 alkylthio, C3-6 cycloalkyl, C3-6 cycloalkyl(C1 4)alkyl, phenyl or benzyl, the phenyl and benzyl groups being optionally substituted with halogen, C14 alkyl or C14 alkoxy.
Substituents which may be present in the aryl or heteroaryl rings of any of the foregoing substituents include one or more of the following; halo, hydroxy, mercapto, C1-4 alkyl, C2-4 alkenyl, C2-4 alkynyl, C1-4 alkoxy, C2-4 alkenyloxy, C2-4 alkynyloxy, halo(C1-4)alkyl, halo(C1-4)alkoxy, C1-4 alkylthio, hydroxy(C1-4)alkyl, C1-4 alkoxy(C1-4)alkyl, C3-6 cycoloalkyl, C3-6 cycloalkyl(C1-4)alkyl, C1-4 alkanoyloxy, benzyloxy, cyano, thiocyanato, nitro, -NR'R", -NHCOR', -NHCONR'R", -CONR'R", -COOR', -OSO2R', -SO2R', -COR', -CR'--NR" or -N=CR'R" in which R' and R" have the meanings given above.
x in formula (I) is a 6-membered aromatic carbonnitrogen heterocycle containing 1 to 3 nitrogen atoms.
Thus X may be pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl or 1,2,3-triazinyl. It is linked to Y, Z and Z1 by any of its carbon atoms.
Y in formula (I) is O, S, CR12 or NR3, wherein R1, R2 and R3 are independently H or C1-4 alkyl. Examples of CR1R2 are CH2 and CHCH3. Examples of NR3 are NH and NCH3.
z in formula (I) has any of the meanings described and elaborated above. Of particular interest, however, are those compounds in which z is optionally substituted aryl or optionally substituted heteroaryl.
In one particular aspect, the invention includes compounds having the formula (I) and stereoisomers thereof, wherein X is 6-Z-pyridin-42-yl, 2-Z-pyridin-4-yl, 5-z-pyridin-3-yl, 4-Z-pyridin-2-yl, 6-Z-pyrimidin-4-yl, 2-z-pyrimidin-4-yl, 4-Z-pyrimidin-2-yl, 5-Z-pyrimidin-2y1, 5-Z-pyrazin-2-yl, 6-z-pyrazin-2-yl, 3-Z-phridazin-5yl, 5-Z-pyridazin-3-yl, 3-Z-1,2,4-triazin-5-yl, 5-Z- 1,2,4-triazin-3-yl or 4-Z-1,3,5-triazin-2-yl; Y is O, S, CH2 or NCH3, Z is phenyl or phenyl substituted with one or more of halo (especially fluoro or chloro), C14 alkyl (especially methyl), C1-4 4 alkoxy (especially methoxy) or cyano; n is 0 or 1 and Z is chloro.
The invention is illustrated by the compounds listed in Table I which follows. Throughout the Table the methyl 3-methoxypropenoate group has the geometry shown in the structural formula at the head of the Table. Where Y is O, S or NR3, it is the (Z)-isomer, and where Y is CR12, it is the (E)-isomer.
TABLE I
Compound (Z1)n Melting No Z-X Y Point ( C) Olefinic* 1 6-Phenylpyridin-2-yl NCH3 2 2-Phenylpyridin-4-yl NCH3 3 5-Phenylpyridin-3-yl NCH3 4 4-Phenylpyridin-2-yl NCH3 5 6-Phenylpyrimidin-4-yl NCH3 6 2-Phenylpyrimidin-4-yl NCH3 7 4-Phenylpyrimidin-2-yl NCH3 8 6-Phenylpyrazin-2-yl NCH3 9 3-Phenylpyridazin-5-yl NCH3 10 5-Phenylpyridazin-3-yl NCH3 11 3-Phenyl-1,2,4-triazin-5-yl NCH3 12 5-Phenyl-1,2,4-triazin-3-yl NCH3 13 4-Phenyl-1,3,5-triazin-2-yl NCH3 (TABLE I (Contd.)
Compound (Z1)n Melting No Z-X Y Point ( C) Olefinic* 14 6-(2-fluorophenyl)pyridin-2-yl NCH3 15 4-(3-cyanophenyl)pyridin-2-yl NCH3 16 6-(4-chlorophenyl)pyrimidin-4-yl NCH3 17 2-(4-methoxyphenyl)pyrimidin-4-yl NCH3 18 4-(4-methylphenyl)pyrimidin-2-yl NCH3 19 5-(4-fluorophenyl)-1,2,4-triazin-3-yl NCH3 20 4-(2-methoxyphenyl)-1,3,5-triazin-2-yl NCH3 21 6-Phenylpyridin-2-yl O 22 4-Phenylpyridin-2-yl O 23 6-Phenylpyrimidin-4-yl O 24 2-Phenylpyrimidin-4-yl O 25 4-Phenylpyrimidin-2-yl O 26 5-Phenyl-1,2,4-triazin-3-yl O 27 4-Phenyl-1,2,4-triazin-2-yl O 28 6-Phenylpyrimidin-4-yl S 29 5-Phenyl-1,2,4-triazin-3-yl S 30 4-Phenyl-1,2,4-triazin-2-yl S 31 6-Phenylpyrimidin-4-yl CH2 TABLE I (Contd.)
Compound (Z1)n Melting No Z-X Y Point ( C) Olefinic* 32 2-Phenylpyrimidin-4-yl CH2 33 4-Phenylpyrimidin-2-yl CH2 34 2-Phenyl-3-chloropyridin-6-yl NCH3 35 6-Methoxypyridin-2-yl NCH3 36 6-Chloropyridin-2-yl NCH3 37 4-Cyanopyfimidin-2-yl O 38 5-Phenylpyrimidin-2-yl NCH3 39 5-Phenylpyrazin-2-yl O 40 6-Phenyl-1,2,4-triazin-3-yl NCH3 41 5-Thien-2-yl-1,2,4-triazin-3-yl NCH3 42 6-Pyrimidin-2-ylpyridin-2-yl S 43 6-Pyridin-2-ylpyridin-2-yl O * Chemical shift of singlet from olefinic proton on 3-methoxypropenoate group (ppm from tetramethylsilane).
Solvent: CDC13 unless otherwise stated.
The compounds of the invention of formula (I) can be made by a variety of methods, some of which are illustrated in Scheme I. Throughout this Scheme, the terms Z, Z1, n, X and Y are as defined above, R is an alkyl group, N is hydrogen or a metal (such as sodium or potassium) and L1 and L2 are leaving groups (preferred values of L1 include fluoride, chloride, bromide and the CH3SO2-anion preferred values of L2 include chloride and bromide). Each of the transformations described in Scheme I is performed at a suitable temperature and either in a suitable solvent or in the absence of a solvent.
Thus compounds of formula (I) can be prepared by treatment of acetates of formula (III) with a base (such as sodium hydride or sodium methoxide) and methyl formate.
If a species of formula CH3L, wherein L is a leaving group such as chloride, bromide, iodide or the CH3O.SO2O-anion, is then added to the reaction mixture, compounds of formula (I) may be obtained. If a protic acid is added to the reaction mixture, compounds of formula (II) wherein M is hydrogen are obtained. Alternatively, the species of formula (II) wherein N is a metal may themselves be isolated from the reaction mixture. Compounds of formula (II) wherein M is a metal can be converted into compounds of formula (I) by treatment with a species of formula CH3L, wherein L is as defined above. Compounds of formula (11) wherein M is hydrogen can be converted into compounds of formula (I) by successive treatments with a base (such as potassium carbonate) and a species of general formula CH3L.
Alternatively, compounds of formula (I) can be prepared from acetals of formula (IV) by elimination of methanol under either acidic or basic conditions.
Examples of reagents or reagent mixtures which can be used for this transformation are lithium di-isopropylamide; potassium hydrogen sulphate (see, for example, T Yamada, H Hagiwara and H Uda, J.Chem.Soc., Chemical Communications, 1980, 838, and references therein); and triethylamine, often in the presence of a Lewis acid such as titanium tetrachloride (see, for example, K Nsunda and L Heresi, J.Chem.Soc., Chemical Communications, 1985, 1000).
Scheme 1
(Zl )n Z-X-Y 1 C 302C CH.OCH3 yr (I) H3 / t 1n 1 (Z1) \ n I I CH Z-X-Y CH3O2C CH(OCH3)2 C (IV) CH3O2C CH.OM ç W (II) zl)n Z-X-Y, I CH::C(oCH3)(0SiR3) 1 (V) z (Zt n Z-X-Y-CH2CO2CH3 (yCRlR2) > (III) ( z 1 + HY-CH2CO2CH3 ( Y&num;CR1R2 ) Z-X-L + HY-CH2C02CH3 z1 (VIII) (VI) (Z1 n + L2 Z-X-YH + L -CH2CO2CH3 (IX) (VII) Acetals of formula (IV) can be prepared by treatment of methyl silyl ketene acetals of formula (V) wherein R is an alkyl group, with trimethyl orthoformate in the presence of a Lewis acid such as titanium tetrachloride (see, for example, K Saigo, M Osaki and T Mukaiyama, Chemistry Letters, 1976, 769).
Methyl silyl ketene acetals of formula (V) can be prepared from acetates of formula (III) by treatment with a base and a trialkylsilyl halide of formula R3SiCl or R3SiBr, such as trimethylsilyl chloride, or a base (such as triethylamine) and a trialkylsilyl triflate of formula R3Si-OSO2CF3 (see, for example, C Ainsworth, F Chen and Y Kuo, J.Organometallic Chemistry, 1972, 46, 59).
It is not always necessary to isolate the intermediates (IV) and (V); under appropriate conditions, compounds of formula (I) may be prepared from acetates of formula (III) in "one pot" by the successive addition of suitable reagents listed above.
Acetates of formula (III) in which Y is oxygen, sulphur or NR3 can be made by reaction between an acetate of formula (VI) and a heterocycle of formula (VIII) or an acetate of formula (VII) and a heterocycle of formula (IX), each generally in the presence of a base (such as sodium hydride or potassium carbonate).
Acetates of formulae (VI) and (VII), heterocycles of formulae (VIII) and (IX) and acetates of formula (III) wherein Y=CR 1R2 may be prepared by methods described in the chemical literature. The substituents Z and zl may be modified at any stage during the process.
Some of these, and other, processes, which may be used for preparing the compounds of formula (I), are further described in EP-A-0383117.
In a further aspect the invention includes processes as hereindefined for preparing compounds of formula (I).
The compounds of the invention are active fungicides and may be used to control one or more of the following pathogens: The compounds are active fungicides and may be used to control one or more of the following pathogens Pyricularia oryzae on rice. Puccinia recondita, Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts e.g. coffee, pears, apples, peanuts, vegetables and ornamental plants. Erysiphe graminis (powdery mildew) on barley and wheat and other powdery mildews on various hosts such as Sphaerotheca macularis on hops, Sphaerotheca fuliginea on cucurbits (e.g. cucumber), Podosphaera leucotricha on apple and Uncinula necator on vines. Helminthosporium spp., Rhynchosporium spp., Septoria spp., Pyrenophora spp., Pseudocercosporella herpotrichoides and Gaeumannomyces graminis on cereals.
Cercospora arachidicola and Cercosporidium personata on peanuts and other Cercospora species on other hosts, for example, sugar beet, bananas, soya beans and rice.
Botrytis cinerea (grey mould) on tomatoes, strawberries, vegetables, vines and other hosts. Alternaria spp. on vegetables (e.g. cucumber), oil-seed rape, apples, tomatoes and other hosts. Venturia inaequalis (scab) on apples. Plasmopara viticola on vines. Other downy mildews such as Bremia lactucae on lettuce, Peronospora spp. on soybeans, tobacco, onions and other hosts, Pseudoperonospora humuli on hops and Pseudoperonospora cubensis on cucurbits. Phytophthora infestans on potatoes and tomatoes and other Phytophthora spp. on vegetables, strawberries, avocado, pepper, ornamentals, tobacco, cocoa and other hosts. Thanatephorus cucumeris on rice and other Rhizoctonia species on various hosts such as wheat and barley, vegetables, cotton and turf.
Some of the compounds show a broad range of activities against fungi in vitro. They may also have activity against various post-harvest diseases of fruit (e.g. Penicillium digitatum and italicum and Trichoderma vi ride on oranges, Gloeosporium musarum on bananas and Botrytis cinerea on grapes).
Further, some of the compounds may be active as seed dressings against pathogens including Fusarium spp., Septoria spp., Tilletia spp., (bunt, a seed-borne disease of wheat), Ustilago spp. and Helminthosporium spp. on cereals, Rhizoctonia solani on cotton and Pyricularia oryzae on rice.
The compounds may move acropetally/locally in plant tissue. Moreover, the compounds may be volatile enough to be active in the vapour phase against fungi on the plant.
The invention therefore provides a method of combating fungi which comprises applying to a plant, to a seed of a plant or to the locus of the plant or seed a fungicidally effective amount of a compound as hereinbefore defined, or a composition containing the same.
The compounds may be used directly for agricultural purposes but are more conveniently formulated into compositions using a carrier or diluent. The invention thus provides fungicidal compositions comprising a compound as hereinbefore defined and an acceptable carrier or diluent therefor.
The compounds can be applied in a number of ways.
For example, they can be applied, formulated or unformulated, directly to the foliage of a plant, to seeds or to other medium in which plants are growing or are to be planted, or they can be sprayed on, dusted on or applied as a cream or paste formulation, or they can be applied as a vapour or as slow release granules.
Application can be to any part of the plant including the foliage, stems, branches or roots, or to soil surrounding the roots, or to the seed before it is planted, or to the soil generally, to paddy water or to hydroponic culture systems. The invention compounds may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods.
The term "plant" as used herein includes seedlings, bushes and trees. Furthermore, the fungicidal method of the invention includes preventative, protectant, prophylactic and eradicant treatments.
The compounds are preferably used for agricultural and horticultural purposes in the form of a composition.
The type of composition used in any instance will depend upon the particular purpose envisaged.
The compositions may be in the form of dustable powders or granules comprising the active ingredient (invention compound) and a solid diluent or carrier, for example, fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, fuller's earth, gypsum, diatomaceous earth and china clay.
Such granules can be preformed granules suitable for application to the soil without further treatment. These granules can be made either by impregnating pellets of filler with the active ingredient or by pelleting a mixture of the active ingredient and powdered filler.
Compositions for dressing seed may include an agent (for example, a mineral oil) for assisting the adhesion of the composition to the seed; alternatively the active ingredient can be formulated for seed dressing purposes using an organic solvent (for example, N-methylpyrrolidone, propylene glycol or dimethylformamide). The compositions may also be in the form of wettable powders or water dispersible granules comprising wetting or dispersing agents to facilitate the dispersion in liquids.
The powders and granules may also contain fillers and suspending agents.
Emulsifiable concentrates or emulsions may be prepared by dissolving the active ingredient in an organic solvent optionally containing a wetting or emulsifying agent and then adding the mixture to water which may also contain a wetting or emulsifying agent. Suitable organic solvents are aromatic solvents such as alkylbenzenes and alkylnaphthalenes, ketones such as cyclohexanone and methylcyclohexanone, chlorinated hydrocarbons such as chlorobenzene and trichlorethane, and alcohols such as benzyl alcohol, furfuryl alcohol, butanol and glycol ethers.
Suspension concentrates of largely insoluble solids may be prepared by ball or bead milling with a dispersing agent with a suspending agent included to stop the solid settling.
Compositions to be used as sprays may be in the form of aerosols wherein the formulation is held in a container under pressure of a propellant, e.g. fluorotrichloromethane or dichlorodifluoromethane.
The invention compounds can be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating in enclosed spaces a smoke containing the compounds.
Alternatively, the compounds may be used in micro-encapsulated form. They may also be formulated in biodegradable polymeric formulations to obtain a slow, controlled release of the active substance.
By including suitable additives, for example additives for improving the distribution, adhesive power and resistance to rain on treated surfaces, the different compositions can be better adapted for various utilities.
The invention compounds can be used as mixtures with fertilisers (e.g. nitrogen-, potassium- or phosphoruscontaining fertilisers). Compositions comprising only granules of fertiliser incorporating, for example coated with, the compound are preferred. Such granules suitably contain up to 25% by weight of the compound. The invention therefore also provides a fertiliser composition comprising a fertiliser and the compound of general formula (I) or a salt or metal complex thereof.
Wettable powders, emulsifiable concentrates and suspension concentrates will normally contain surfactants, e.g. a wetting agent, dispersing agent, emulsifying agent or suspending agent. These agents can be cationic, anionic or non-ionic agents.
Suitable cationic agents are quaternary ammonium compounds, for example, cetyltrimethylammonium bromide.
Suitable anionic agents are soaps, salts of aliphatic monoesters of sulphuric acid (for example, sodium lauryl sulphate), and salts of sulphonated aromatic compounds (for example, sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of sodium diisopropyl- and triisopropyl- naphthalene sulphonates).
Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkyl phenols such as octyl- or nonylphenol and octylcresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of the said partial esters with ethylene oxide, and the lecithins. Suitable suspending agents are hydrophilic colloids (for example, polyvinylpyrrolidone and sodium carboxymethylcellulose), and swelling clays such as bentonite or attapulgite.
Compositions for use as aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being diluted with water before use. These concentrates should preferably be able to withstand storage for prolonged periods and after such storage be capable of dilution with water in order to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may conveniently contain up to 95%, suitably 10-85%, for example 25-60%, by weight of the active ingredient. After dilution to form aqueous preparations, such preparations may contain varying amounts of the active ingredient depending upon the intended purpose, but an aqueous preparation containing 0.0005% or 0.01% to 10% by weight of active ingredient may be used.
The compositions of this invention may contain other compounds having biological activity, e.g. compounds having similar or complementary fungicidal activity or which possess plant growth regulating, herbicidal or insecticidal activity.
A fungicidal compound which may be present in the composition of the invention may be one which is capable of combating ear diseases of cereals (e.g. wheat) such as Septoria, Gibberella and Helminthosporium spp., seed and soil-borne diseases and downy and powdery mildews on grapes and powdery mildew and scab on apple, etc. By including another fungicide, the composition can have a broader spectrum of activity than the compound of general formula (I) alone. Further the other fungicide can have a synergistic effect on the fungicidal activity of the compound of general formula (I).Examples of fungicidal compounds which may be included in the composition of the invention are (RS)-1-aminopropylphosphonic acid, (RS)-4 (4-chlorophenyl)-2-phenyl-2-(lH-1,2,4-triazol-1-yl- methyl)butyronitrile, (Z)-N-but-2-enyloxymethyl-2-chloro2',6'-diethylacetanilide, l-(2-cyano-2-methoxyiminoacetyl)-3-ethyl urea, 1-[(2RS,4RS; ;2RS,4RS)-4-bromo-2 (2,4-dichlorophenyl)tetrahydrofurfuryl]-1H-1,2,4-triazole, 3-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)- quinazolin-4(3H)-one, 3-chloro-4-[4-methyl-2-(1H-1,2,4- triazol-1-methyl )-1 , 3-dioxolan-2-yl ]phenyl-4-chlorophenyl ether, 4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenz- imidazole-1-sulphonamide, 5-ethyl-5,8-dihydro-8-oxo(1,3) dioxolo(4,5-p)quinoline-7-carboxylic acid, a-[N-(3- chloro-2,6-xylyl)-2-methoxyacetamido]-y-butyrolactone, aldimorph, anilazine, benalaxyl, benomyl, biloxazol, binapacryl, bitertanol, blasticidin S, bupirimate, buthiobate, captafol, captan, carbendazim, carboxin, chlorbenz-thiazone, chloroneb, chlorothalonil, chlorozolinate, copper containing compounds such as copper oxychloride, copper sulphate and Bordeaux mixture, cycloheximide, cymoxanil, cyproconazole, cyprofuram, di-2-pyridyl disulphide 1,1'-dioxide, dichlofluanid, dichlone, diclobutrazol, diclomezine, dicloran, difenoconazole, dimethamorph, dimethirimol, diniconazole, dinocap, ditalimfos, dithianon, dodemorph, dodine, edifenphos, etaconazole, ethirimol, ethyl (Z)-N-benzyl-N-( [methyl(methylthioethylideneamino-oxy- carbonyl)amino]thio)-B-alaninate, etridiazole, fenapanil, fenarimol, fenfuram, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, flutolanil, flutriafol, flusilazole, folpet, fosetyl-aluminium, fuberidazole, furalaxyl, furconazole-cis, guazatine, hexaconazole, hydroxyisoxazole, imazalil, imibenconazole, iprobenfos, iprodione, isoprothiolane, kasugamycin, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, methfuroxam, metsulfovax, myclobutanil, N-( 4-methyl-6-prop-1- ynylpyrimidin-2-yl)aniline, neoasozin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, organomercury compounds, oxadixyl, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phthalide, polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, prothiocarb, pyrazophos, pyrifenox, pyroquilon, pyroxyfur, pyrrolnitrin, quinomethionate, quintozene, SSF-109, streptomycin, sulphur, tebuconazole, techlofthalam, tecnazene, tetra-conazole, thiabendazole, thicyofen, thiophanate-methyl, thiram, tolclofos-methyl, triacetate salt of l,l-iminodi(octa-methylene)diguanidine, triadimefon, triadimenol, triazbutyl, tricyclazole, tridemorph, triforine, validamycin A, vinclozolin, zarilamid and zineb. The compounds of general formula (I) can-be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.
Suitable insecticides which may be incorporated in the composition of the invention include buprofezin, carbaryl, carbofuran, carbosulfan, chlorpyrifos, cycloprothrin, demeton-s-methyl, diazinon, dimethoate, ethofenprox, fenitrothion, fenobucarb, fenthion, formothion, isoprocarb, isoxathion, monocrotophos, phenthoate, pirimicarb, propaphos and XMC.
Plant growth regulating compounds are compounds which control weeds or seedhead, formation, or selectively control the growth of less desirable plants (e.g.
grasses).
Examples of suitable plant growth regulating compounds for use with the invention compounds are 3,6-dichloropicolinic acid, 1-(4-chlorophenyl)-4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylic acid, methyl-3,6-dichloroanisate, abscisic acid, asulam, benzoylprop-ethyl, carbetamide, daminozide, difenzoquat, dikegulac, ethephon, fenpentezol, fluoridamid, glyphosate, glyphosine, hydroxybenzonitriles (e.g. bromoxynil), inabenfide, isopyrimol, long chain fatty alcohols and acids, maleic hydrazide, mefluidide, morphactins (e.g.
chlorfluoroecol), paclobutrazol, phenoxyacetic acids (e.g.
2,4-D or MCPA), substituted benzoic acid (e.g. triiodobenzoic acid), substituted quaternary ammonium and phosphonium compounds (e.g. chloromequat, chlorphonium or mepiquatchloride), tecnazene, the auxins (e.g.
indoleacetic acid, indolebutyric acid, naphthylacetic acid or naphthoxyacetic acid), the cytokinins (e.g.
benzimidazole, benzyladenine, benzylaminopurine, diphenylurea or kinetin), the gibberellins (e.g. GA3, GA4 or GA7) and triapenthenol.
The following are examples of compositions suitable for agricultural and horticultural proposes which can be formulated from the compounds of the invention. Such compositions form another aspect of the invention.
Percentages are by weight.
EXAMPLE 1 An emulsifiable concentrate is made up by mixing and stirring the ingredients until all are dissolved.
Compound No. 1 of Table I 10% Benzyl alcohol 30% Calcium dodecylbenzenesulphonate 5% Nonylphenolethoxylate (13 mole ethylene oxide) 10% Alkyl benzenes 45% EXAMPLE 2 The active ingredient is dissolved in methylene chloride and the resultant liquid sprayed on to the granules of attapulgite clay. The solvent is then allowed to evaporate to produce a granular composition.
Compound No. 2 of Table I 5% Attapulgite granules 95% EXAMPLE 3 A composition suitable for use as a seed dressing is prepared by grinding and mixing the three ingredients.
Compound No. 3 of Table I 50% Mineral oil 2% China clay 48% EXAMPLE 4 A dustable powder is prepared by grinding and mixing the active ingredient with talc.
Compound No. 4 of Table I 5% Talc 95% EXAMPLE 5 A suspension concentrate is prepared by ball milling the ingredients to form an aqueous suspension of the ground mixture with water.
Compound No. 5 of Table I 40% Sodium lignosulphonate 10% Bentonite clay 1% Water 49% This formulation can be used as a spray by diluting into water or applied directly to seed.
EXAMPLE 6 A wettable powder formulation is made by mixing together and grinding the ingredients until all are throughly mixed.
Compound No. 6 of Table I 25% Sodium lauryl sulphate 2% Sodium lignosulphonate 5% Silica 25% China clay 43% EXAMPLE 7 The compounds are tested against a variety of foliar fungal diseases of plants. The technique employed is as follows.
The plants are grown in John Innes Potting Compost (no 1 or 2) in 4cm diameter minipots. The test compounds are formulated either by bead milling with aqueous Dispersol T or as a solution in acetone or acetone/ethanol which is diluted to the required concentration immediately before use. For the foliage diseases, the formulations (100 ppm active ingredient except where otherwise indicated) are sprayed onto the foliage and applied to the roots of the plants in the soil. The sprays are applied to maximum retention and the root drenches to a final concentration equivalent to approximately 40 ppm a.i. in dry soil. Tween 20, to give a final concentration of 0.05%, is added when the sprays are applied to cereals.
For most of the tests the compound is applied to the soil (roots) and to the foliage (by spraying) one or two days before the plant is inoculated with the disease. An exception is the test on Erysiphe graminis in which the plants are inoculated 24 hours before treatment. Foliar pathogens were applied by spray as spore suspensions onto the leaves of test plants. After inoculation, the plants are put into an appropriate environment to allow infection to proceed and then incubated until the disease is ready for assessment. The period between inoculation and assessment varies from four to fourteen days according to the disease and environment.
The disease control is recorded by the following grading: 4 - no disease 3 . trace-5% of disease on untreated plants 2 = 6-25% of disease on untreated plants 1 1 26-59% of disease on untreated plants 0@ 60-100% of disease on untreated plants

Claims (4)

  1. CLAIMS 1. Compounds having the formula (I):
    and stereoisomers thereof, wherein X is a 6-membered aromatic carbon-nitrogen heterocycle containing 1 to
    3 nitrogen atoms and linked to Y, Z and Z1 by any of its carbon atoms, or a N-oxide derivative thereof; Y is O, S, CR1R2 or NR3, wherein R1, R2 and R3 are independently H or C1-4 alkyl;Z is H, halo, hydroxy, optionally substituted alkoxy, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylthio, optionally substituted heteroaryl, optionally substituted heteroaryloxy, optionally substituted heteroarylthio, optionally substituted acyloxy, optionally substituted amino, optionally substituted arylazo, optionally substituted acylamino, nitro, cyano, -CO2R4, -CONR4R5, -COR4, -CR4=NR5, -N=CR4R5 or -S(O)mR4, wherein m is 0, 1 or 2; and R4 and R5, which are the same or different, are H, alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl or optionally substituted aryl; Z1 is halo, hydroxy, methyl, halomethyl, methoxy, halomethoxy, cyano, nitro, amino, methylamino or dimethylamino; n is 0, 1, 2 or 3; and, when n is 2 or 3, the values of z may be the same or different.
  2. 2. Processes for preparing compounds according to claim
    1 as herein described.
  3. 3. A fungicidal composition comprising a fungicidally effective amount of a compound according to claim 1 and a fungicidally acceptable carrier or diluent therefor.
  4. 4. A method of combating fungi which comprises applying to plants, to the seeds of plants or to the locus of the plants or seeds, a compound according to claim 1 or a composition according to claim 3.
GB9023018A 1989-11-22 1990-10-23 Methyl 2-substituted-3-methoxy-2-propenoates as fungicides Withdrawn GB2238308A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB898926429A GB8926429D0 (en) 1989-11-22 1989-11-22 Fungicides

Publications (2)

Publication Number Publication Date
GB9023018D0 GB9023018D0 (en) 1990-12-05
GB2238308A true GB2238308A (en) 1991-05-29

Family

ID=10666740

Family Applications (2)

Application Number Title Priority Date Filing Date
GB898926429A Pending GB8926429D0 (en) 1989-11-22 1989-11-22 Fungicides
GB9023018A Withdrawn GB2238308A (en) 1989-11-22 1990-10-23 Methyl 2-substituted-3-methoxy-2-propenoates as fungicides

Family Applications Before (1)

Application Number Title Priority Date Filing Date
GB898926429A Pending GB8926429D0 (en) 1989-11-22 1989-11-22 Fungicides

Country Status (1)

Country Link
GB (2) GB8926429D0 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0503436A1 (en) * 1991-03-13 1992-09-16 Bayer Ag Triazinyl substituted acrylic acid esters
EP0579908A2 (en) * 1992-05-11 1994-01-26 Bayer Ag Pyridyl derivatives, process for their preparation and their use as pesticides
EP0584625A1 (en) * 1992-08-21 1994-03-02 Bayer Ag Pyridyloxy substituted esters of acrylic acid
US5371095A (en) * 1990-02-08 1994-12-06 Bayer Aktiengesellschaft Pyridyl compounds which have pesticidal activity
WO1996035669A1 (en) * 1995-05-09 1996-11-14 Basf Aktiengesellschaft (het)aryloxy-, -thio-, aminocrotonates, methods of preparing them and their use as insecticides and fungicides
EP0634405B1 (en) * 1993-07-12 2002-10-30 Bayer Aktiengesellschaft Pyrimidinyl acrylic acid derivatives, process for their preparation and their use for the control of phytopathogens

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0383117A2 (en) * 1989-02-17 1990-08-22 Bayer Ag Pyridine-substituted esters of acrylic acid
GB2229720A (en) * 1986-08-20 1990-10-03 Ici Plc Fungicides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2229720A (en) * 1986-08-20 1990-10-03 Ici Plc Fungicides
EP0383117A2 (en) * 1989-02-17 1990-08-22 Bayer Ag Pyridine-substituted esters of acrylic acid

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5371095A (en) * 1990-02-08 1994-12-06 Bayer Aktiengesellschaft Pyridyl compounds which have pesticidal activity
EP0503436A1 (en) * 1991-03-13 1992-09-16 Bayer Ag Triazinyl substituted acrylic acid esters
US5238934A (en) * 1991-03-13 1993-08-24 Bayer Aktiengesellschaft Triazinyl-substituted acrylic esters
EP0579908A2 (en) * 1992-05-11 1994-01-26 Bayer Ag Pyridyl derivatives, process for their preparation and their use as pesticides
EP0579908A3 (en) * 1992-05-11 1994-02-02 Bayer Ag Pyridyl derivatives, process for their preparation and their use as pesticides
EP0584625A1 (en) * 1992-08-21 1994-03-02 Bayer Ag Pyridyloxy substituted esters of acrylic acid
US5580868A (en) * 1992-08-21 1996-12-03 Bayer Aktiengesellschaft Pyridyloxy-acrylic acid esters
EP0634405B1 (en) * 1993-07-12 2002-10-30 Bayer Aktiengesellschaft Pyrimidinyl acrylic acid derivatives, process for their preparation and their use for the control of phytopathogens
WO1996035669A1 (en) * 1995-05-09 1996-11-14 Basf Aktiengesellschaft (het)aryloxy-, -thio-, aminocrotonates, methods of preparing them and their use as insecticides and fungicides
US5985919A (en) * 1995-05-09 1999-11-16 Basf Aktiengesellschaft (Het)aryloxy-, -thio- , aminocrotonates, methods of preparing them and their use as insecticides and fungicides

Also Published As

Publication number Publication date
GB9023018D0 (en) 1990-12-05
GB8926429D0 (en) 1990-01-10

Similar Documents

Publication Publication Date Title
EP0569384B2 (en) Fungicides
EP0370629B2 (en) Fungicides
US5238956A (en) Fungicidal aromatic dioxime
EP0586393B1 (en) Substituted-2-phenyl-3-methoxypropenoates as fungicides
EP0260794A2 (en) Substituted phenyl-2-propenoic acid derivatives and their use as fungicides
EP0468684B1 (en) Propenoic acid derivatives, process for their preparation and their use as fungicides
EP0393861B1 (en) Fungicides
EP0341845B1 (en) Fungicides
EP0405782B1 (en) Fungicides
US5185339A (en) Fungicidal compounds
IE75219B1 (en) Pyridyl cyclopropane derivatives with fungicidal activity
GB2238308A (en) Methyl 2-substituted-3-methoxy-2-propenoates as fungicides
EP0557291B1 (en) Pyridil-pyrimidine derivatives as fungicidal compounds
EP0291196B1 (en) Fungicides
EP0430471B1 (en) Fungicides
US5153199A (en) Fungicidal compounds
EP0483985B1 (en) Fungicides
IE903324A1 (en) Fungicides
GB2249092A (en) Oxime ether fungicides
US5100886A (en) Metal complexes of pyridyl cyclopropane carboxamide compounds which are useful as fungicides
US5229391A (en) Pyrimidine derivatives and their use as fungicidal agents
EP0422848A1 (en) Fungicides

Legal Events

Date Code Title Description
WAP Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1)