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WO1999067209A1 - Hydroximic acid derivatives, process for their preparation and intermediates therefor - Google Patents

Hydroximic acid derivatives, process for their preparation and intermediates therefor Download PDF

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Publication number
WO1999067209A1
WO1999067209A1 PCT/GB1999/001664 GB9901664W WO9967209A1 WO 1999067209 A1 WO1999067209 A1 WO 1999067209A1 GB 9901664 W GB9901664 W GB 9901664W WO 9967209 A1 WO9967209 A1 WO 9967209A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
optionally substituted
compound according
compound
halogen
Prior art date
Application number
PCT/GB1999/001664
Other languages
French (fr)
Inventor
Daniel Rees Allen
Geoffrey Gower Briggs
Clive Leonard Cornell
Darren James Mansfield
Peter John West
Original Assignee
Hoechst Schering Agrevo Gmbh
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
Priority claimed from GBGB9813269.9A external-priority patent/GB9813269D0/en
Priority claimed from GBGB9902137.0A external-priority patent/GB9902137D0/en
Application filed by Hoechst Schering Agrevo Gmbh filed Critical Hoechst Schering Agrevo Gmbh
Priority to AU43777/99A priority Critical patent/AU4377799A/en
Publication of WO1999067209A1 publication Critical patent/WO1999067209A1/en

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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
    • C07D213/60—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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
    • 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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
    • C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
    • C07C259/06—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/14—Dithiocarbamic acids; Derivatives thereof
    • C07C333/18—Esters of dithiocarbamic acids
    • C07C333/24—Esters of dithiocarbamic acids having nitrogen atoms of dithiocarbamate groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C337/00—Derivatives of thiocarbonic acids containing functional groups covered by groups C07C333/00 or C07C335/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
    • C07C337/02—Compounds containing any of the groups, e.g. thiocarbazates
    • C07C337/04—Compounds containing any of the groups, e.g. thiocarbazates the other nitrogen atom being further doubly-bound to a 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
    • C07D213/61—Halogen atoms or nitro radicals
    • 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
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/06—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D277/24—Radicals substituted by oxygen atoms
    • 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
    • C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te

Definitions

  • This invention relates to processes, intermediates in the processes and compounds obtainable by the processes. Many of the compounds have pesticidal, 5 especially fungicidal, insecticidal and acancidal, activity.
  • X is oxygen or sulfur
  • Y is alkyl, alkenyl, alkynyl or cycloalkyl, each of which may be substituted, or is hydrogen; Z is as defined for Y or is an optionally substituted alkoxy or optionally substituted ammo group; R is an organic group, preferably an optionally substituted aromatic carbo- or heterocyclyl group; and L is a leaving group, for example halogen, -OSO2Q or -S(0)qQ where Q is an optionally substituted alkyl or optionally substituted carbocyclyl group and q is 1 or 2; preferably L is -SO2Q where Q is C - ] -C5 optionally substituted alkyl or optionally substituted phenyl, especially C -1 -C5 alkyl or phenyl.
  • X, Y and Z are as defined above; X preferably being oxygen; Y preferably being methyl, cyanomethyl, t ⁇ fluoromethyl, difluoromethyl, monofluoromethyl (especially methyl); and Z preferably being methoxy or monomethyiamino, especially monomethyiamino; each R ⁇ , which may be the same or different to any other R ⁇ , is alkyl, alkenyl, alkynyl, or cycloalkyl, each of which may be substituted, or is alkoxy, haloalkoxy, halogen, nitro or cyano; R ⁇ is preferably C-1-C5 alkyl (especially methyl) or halogen (especially chlorine or fluorine); m is 0 to 4, preferably 0 or 1;
  • R 2 IS alkyl, alkenyl, alkynyl, carbocyclyl or heterocyciyl, each of which may be substituted, or is hydrogen or Si(R >3, where R 3 IS alkyl, phenyl, alkoxy or haloalkoxy;
  • R 2 is preferably optionally substituted phenyl (preferred substituents are C1-C5 alkyl, halogen, haloalkyl or haloalkoxy) or optionally substituted aromatic heterocyciyl (preferred substituents are C1-C alkyl, halogen, haloalkyl, haloalkoxy, optionally substituted phenyl or optionally substituted phenoxy, especially unsubstituted phenyl or halophenyl);
  • a 4 ⁇ s-0-N C(R 5 )-
  • X 1 is 0, S, NR 6 or a direct bond
  • X 2 is O, NR 6 or a direct bond
  • R 4 which may be the same or different to any other R 4 , is alkyl, cycloalkyl or phenyl, each of which may be substituted (preferably by alkyl, phenyl or halogen), or is hydrogen, halogen or cyano; R 4 is preferably hydrogen or C- ] -C5 alkyl (especially methyl);
  • R 3 which may be the same or different to any other R°, is alkyl, alkenyl, alkynyl, alkoxy, alkylthio, each of which may be substituted (preferably by halogen), carbo- or hetero-cyclyl which may be substituted (preferably by alkyl or halogen), or is hydrogen;
  • R ⁇ IS preferably hydrogen or C 1 -C5 alkyl (especially methyl);
  • R° which may be the same or different to any other R" is optionally substituted alkyl (preferably by halogen) or optionally substituted carbo- or heterocyciyl (preferably by alkyl, phenyl or halogen) , or is hydrogen, or two R ⁇ groups on A, together with the connecting atoms, form a 5 to 7 membered ring;
  • R ⁇ is preferably C 1 -C5 alkyl; where the moiety depicted on the right side of linkage A is attached to R 2 , or -A-R 2 and R 1 together with benzene ring M form an optionally substituted fused ring system.
  • Preferred linkages A are: a direct bond, -0-, -C ⁇ C-, -A 1 -, -A 4 -, -A 1 0-, -OA 1 -, -A 1 -A 4 - or -A 1 -A 4 -A 3 -.
  • Particularly preferred linkages are: a direct bond, -0-, -C ⁇ C-, -A 1 - or -A 1 0-.
  • R 1 is para to the -A-R 2 group.
  • R 2 is phenyl or aromatic heterocyciyl, each of which may be substituted (preferably by C 1 -C5 alkyl, halogen, haloalkyl, haloalkoxy, optionally substituted phenyl or optionally substituted phenoxy).
  • R 2 is preferably phenyl optionally substituted by C 1 -C5 alkyl, halogen, haloalkyl or haloalkoxy, or R 2 is aromatic heterocyciyl (preferably th ⁇ azol-2-yl or 1 ,2,4- oxad ⁇ azol-3-yl) optionally substituted by C1 -C5 alkyl, halogen, haloalkyl, haloalkoxy or phenyl optionally substituted by halogen.
  • A is -0-, -C ⁇ C-,
  • R 2 is preferably phenyl optionally substituted by C -1 -C5 alkyl, halogen, haloalkyl, haloalkoxy or optionally substituted phenoxy
  • Any alkyl group present in the molecule may be straight or branched and is preferably of 1 to 1 0 carbon atoms, especially 1 to 7 and particularly 1 to 5 carbon atoms.
  • Any alkenyl or alkynyl group may be straight or branched and is preferably of 2 to 7 carbon atoms and up to 3 double or triple bonds which may be conjugated, for example vinyl, allyl, butadienyl or propargyl
  • carbocyclyl includes saturated carbocyclic groups; unsaturated carbocyclic groups having up to 3 double bonds which may be conjugated; and aromatic carbocyclic groups, e.g. phenyl Carbocyclic groups are typically 3 to 8 membered rings
  • carbocyclyl includes fused carbocyclyl groups, e g napthalene, phenanthrene, indane and indene.
  • heterocyciyl includes both aromatic and non-aromatic heterocyciyl groups
  • Heterocyciyl groups are generally 5 6 or 7-membered rings containing up to 4 hetero-atoms selected from nitrogen oxygen and sulfur.
  • heterocyciyl groups are furyl, thienyl, pyrrolyl, pyrrolinyl, pyrroiidinyl, imidazolyl, dioxolanyl, oxazolyl, thiazolyl, imidazolyl, imidazolinyl, imidazolidinyl, pyrazolyl, pyrazoiinyl, pyrazolidinyl, isoxazolyi, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, pyranyl, py ⁇ dyl, pipe ⁇ dinyl, dioxanyi, morpholino, dithianyl, thiomorphoiino, py ⁇ dazinyl, py ⁇ midinyl, pyrazmyl, piperazinyl, sulfolanyl, tetrazolyl, t ⁇ azinyl, azepinyl,
  • heterocyciyl includes fused heterocyciyl groups, for example benzimidazolyl, benzoxazolyl, imidazopy ⁇ dinyl, benzoxazinyl, benzothiazinyl, oxazolopy ⁇ dinyl, benzofuranyi, quinolmyl, quinazo nyl, quinoxalinyl, dihydroquinazolinyl, benzothiazolyl, phthalimido, benzofuranyi, benzodiazepinyl, indolyl and isomdolyl Any alkyl, alkenyl, alkynyl, carbocyclyl, heterocyciyl group, alkoxy or alkylthio group when substituted, may be substituted by at least one group, which may be the same or different, and may be selected from the group: nitro, halogen, cyano, acyl, -O-acyl, -S-acyl
  • Any ammo group when substituted may be substituted by one or two optionally substituted alkyl or acyl groups, or two substituents together with the nitrogen to which they are attached may form a heterocyciyl group, preferably a 5 to 7- membered heterocyciyl group, which may be substituted and may contain other hetero atoms, for example morpholino, thiomorpholmo or pipe ⁇ dinyl.
  • acyl includes the residue of sulfur and phosphorus-containing acids as well as carboxy c acids.
  • the invention includes individual isomers as well as mixtures thereof.
  • the invention includes individual tautomers as well as mixtures thereof.
  • the compounds of the invention have activity as fungicides, especially against fungal diseases of plants, e.g. mildews and particularly barley powdery mildew (Erys ⁇ he graminis) and vine downy mildew (Plasmopara viticola), rice blast ⁇ Pyncularia oryzae), cereal eyespot (Pseudocercosporella herpotnchoides), rice sheath blight [Pe/licu/ana sasakii), grey mould (Botrytis cinerea), damping off ⁇ Rhizoctonia solani), wheat brown rust (Puccinia recondita), late tomato or potato blight (Phytophthora infestans), apple scab ⁇ Ventuna inaequahs), glume blotch (Leptosphaena nodorum) .
  • the compounds of the invention also have insecticidal, aca ⁇ cidal and nematicidal activity and are particularly useful in combating a variety of economically important insects, acarids and plant nematodes, including animal ectoparasites and especially Diptera, such as sheep blow-fly, Lucilia sencata, and house-flies, Musca domestica; Lepidoptera, including Plutella xylostella, Spodoptera littoralis, Heliothis armigera and Piens brassicae, Homoptera, including aphids such as Megoura viciae; Coleoptera, including corn rootworms [Diabrotica spp., e.g. Diabrotica undecimpunctata) , and spider mites, such as Tetranychus spp.
  • Diptera such as sheep blow-fly, Lucilia sencata, and house-flies, Musca domestica
  • Lepidoptera including Plutella xy
  • the invention thus also provides a method of combating pests (i.e. fungi, insects, nematodes, acarids and weeds) at a locus infested or liable to be infested therewith, which comprises applying to the locus a compound of formula I
  • the invention also provides an agricultural composition
  • an agricultural composition comprising a compound of formula I in admixture with an agriculturally acceptable diluent or carrier.
  • composition of the invention may of course include more than one compound of the invention.
  • composition can comprise one or more additional active ingredients, for example compounds known to possess plant-growth regulant, herbicidal, fungicidal, insecticidal or aca ⁇ cidal properties.
  • additional active ingredients for example compounds known to possess plant-growth regulant, herbicidal, fungicidal, insecticidal or aca ⁇ cidal properties.
  • the compound of the invention can be used in sequence with the other active ingredient.
  • the diluent or carrier in the composition of the invention can be a solid or a liquid optionally in association with a surface-active agent, for example a dispersing agent, emulsifying agent or wetting agent.
  • Suitable surface-active agents include anionic compounds such as a carboxylate, for example a metal carboxylate of a long chain fatty acid, an N-acylsarcosinate; mono- or di-esters of phosphoric acid with fatty alcohol ethoxylates or salts of such esters; fatty alcohol sulfates such as sodium dodecyl sulfate, sodium octadecyl sulfate or sodium cetyl sulfate; ethoxylated fatty alcohol sulfates, ethoxylated alkylphenol sulfates, lignm sulfonates, petroleum sulfonates, alkyl-aryl sulfonates such as alkyl-benzene s
  • butyl-naphthalene sulfonate salts of sulfonated naphthalene-formaldehyde condensates, salts of sulfonated phenol-formaldehyde condensates, or more complex sulfonates such as the amide sulfonates, e.g. the sulfonated condensation product of oleic acid and N-methyl tau ⁇ ne or the dialkyl sulfosuccmates, e.g.
  • Nonionic agents include condensation products of fatty acid esters, fatty alcohols, fatty acid amides or fatty-alkyl- or alkenyl-substituted phenols with ethylene oxide, fatty esters of polyhyd ⁇ c alcohol ethers, e g sorbitan fatty acid esters, condensation products of such esters with ethylene oxide, e.g polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, acetylenic glycols such as 2,4,7,9-tetramethyl-5-decyne- 4,7-d ⁇ ol, or ethoxylated acetylenic glycols.
  • a cationic surface-active agent examples include, for instance, an aliphatic mono-, d ⁇ -, or polyamine as an acetate, naphthenate or oleate, an oxygen-containing amme such as an amme oxide or polyoxyethylene alkylamme, an amide-linked amme prepared by the condensation of a carboxy c acid with a di- or polyamine; or a quaternary ammonium salt.
  • compositions of the invention can take any form known in the art for the formulation of agrochemicals, for example, a solution, a dispersion, an aqueous emulsion, a dusting powder, a seed dressing, a fumigant, a smoke, a dispersible powder, an emulsifiable concentrate or granules. Moreover it can be in a suitable form for direct application or as a concentrate or primary composition which requires dilution with a suitable quantity of water or other diluent before application.
  • An emulsifiable concentrate comprises a compound of the invention dissolved in a water-immiscibie solvent which is formed into an emulsion with water in the presence of an emulsifying agent.
  • a dusting powder comprises a compound of the invention intimately mixed and ground with a solid pulverulent diluent, for example, kaolin.
  • a granular solid comprises a compound of the invention associated with similar diluents to those which may be employed in dusting powders, but the mixture is granulated by known methods. Alternatively it comprises the active ingredient absorbed or adsorbed on a pre-granular diluent, for example, Fuller's earth, attapulgite or limestone grit.
  • Wettable powders, granules or grains usually comprise the active ingredient in admixture with a suitable surfactant and an inert powder diluent such as china clay
  • Another suitable concentrate is a flowable suspension concentrate which is formed by grinding the compound with water or other liquid, a wetting agent and a suspending agent.
  • the concentration of the active ingredient in the composition of the present invention, as applied to plants is preferably within the range of 0.0001 to 1 .0 per cent by weight, especially 0.0001 to 0.01 per cent by weight.
  • the amount of active ingredient can vary widely and can be, for example, from 5 to 95 per cent by weight of the composition.
  • the compound is generally applied to seeds, plants or their habitat
  • the compound can be applied directly to the soil before, at or after drilling so that the presence of active compound in the soil can control the growth of fungi which may attack seeds.
  • the active compound can be applied in any manner which allows it to be intimately mixed with the soil such as by spraying, by broadcasting a solid form of granules, or by applying the active ingredient at the same time as drilling by inserting it in the same drill as the seeds.
  • a suitable application rate is within the range of from 5 to 1 000 g per hectare, more preferably from 1 0 to 500 g per hectare.
  • the active compound can be applied directly to the plant by, for example, spraying or dusting either at the time when the fungus has begun to appear on the plant or before the appearance of fungus as a protective measure.
  • the preferred mode of application is by foliar spraying. It is generally important to obtain good control of fungi in the early stages of plant growth as this is the time when the plant can be most severely damaged.
  • the spray or dust can conveniently contain a pre- or post-emergence herbicide if this is thought necessary.
  • a suitable rate of application is from 0.025 to 5 kg per hectare, preferably from 0.05 to 1 kg per hectare.
  • the compounds of the invention can be applied to plants or parts thereof which have been genetically modified to exhibit a trait such as fungal, insect and/or herbicidal resistance.
  • compounds of formula III where Z is not an amino group containing a free NH may be prepared from iminoyl chlorides according to Scheme 2.
  • L is a leaving group such as halogen or sulfonate.
  • Compounds of formula la may be prepared by reacting compounds of formula IV under basic condition with compounds of formula III according to Scheme 4
  • Preferred basic conditions comprise an alkali metal hydride in a suitable solvent, such as tetrahydrofuran, or a weak base such as sodium carbonate in a suitable solvent, such as methylethyl ketone Scheme 4
  • -CHR 4 X- group wherein the carbon is attached to benzene ring M may be prepared according to Scheme 5
  • Compounds of formula lc are reacted under basic conditions, with R 2 XH, where R 2 XH includes alcohols, phenols, thiophenols, mercaptans, oximes, amides, thioamides etc.
  • Preferred basic conditions comprise an alkali metal hydride in a suitable solvent, e.g. tetrahydrofuran Scheme 5
  • R ⁇ , R 2 and A may be introduced either before or after reaction of IV with III in Scheme 4
  • Q1 IS iodine, with a boronic acid R -B(OH>2, sodium carbonate, a catalytic amount of palladium catalyst such as tetrakis (tr ⁇ phenyiphosph ⁇ ne)pallad ⁇ um (0) in a two phase system such as toluene, methanol and water at conditions between room temperature and reflux.
  • a boronic acid R -B(OH>2, sodium carbonate a catalytic amount of palladium catalyst such as tetrakis (tr ⁇ phenyiphosph ⁇ ne)pallad ⁇ um (0) in a two phase system such as toluene, methanol and water at conditions between room temperature and reflux.
  • Compounds of formula Ih i.e. compounds of formula la where A is a direct bond and R 2 is polyfluoroalkyl, may be prepared by reacting compounds of formula Ig with a polyfluoroalkyl iodide in the presence of a copper catalyst according to
  • Scheme 8 Preferred conditions involve reacting Ig, where Q 2 is iodide, with polyfuororalkyl iodide and copper-bronze in dry dimethyl sulfoxide solvent at 1 30 °C.
  • Compounds of formula Ij i.e. compounds of formula la where A is -C ⁇ C-, may be prepared by a variety of routes.
  • a preferred route involves reacting a compound of formula Ig with a terminal acetylene V in the presence of palladium catalyst, a tertiary amme, a tertiary phosphine and a copper salt in an aprotic solvent. Typical conditions are shown in Scheme 9 Scheme 9
  • Methoxyl amme hydrochlo ⁇ de (20 g) was suspended in dichloromethane ( 1 50 ml) . T ⁇ ethylamine (25 g) was added and the mixture stirred for 20 mins at room temperature. Methyl oxalyl chloride (30 g) was then added dropwise whilst maintaining the temperature between 20-25 °C. The mixture was stirred for 2 hours at room temperature. T ⁇ ethylamine (25 g) was then added dropwise over 20 mins, and the solution stirred for a further 20 mins. The solvent was removed in vacuo, and the residue triturated with ether.
  • Plasmopara viticola vine downy mildew
  • Erysiphe graminis f. sp. tritici wheat powdery mildew
  • Leptosphae a nodorum glume blotch Aqueous solutions or dispersions of the compounds at the desired concentration, including a wetting agent, were applied by spray or by drenching the stem base of the test plants, as appropriate. After a given time, plants or plant parts were inoculated with appropriate test pathogens before or after application of the compounds as appropriate, and kept under controlled environmental 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 are assessed on a score of 1 to 3 where 1 is little or no control, 2 is moderate control and 3 is good to total control. At a concentration of 500 ppm (w/v) or less, the following compounds scored 2 or more against the fungi specified.
  • Plasmopara viticola 64, 66-72, 78, 82, 88, 94, 104, 114, 120-125, 127, 145, 146, 158, 164, 165, 184, 186, 188, 217 and 222.

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Abstract

There is disclosed a process for preparing compounds of formula (I) comprising reacting a compound of formula (II): R-X-H, under basic conditions, with a compound of formula (III), wherein X is oxygen or sulfur; Y is alkyl, alkenyl, alkynyl or cycloalkyl, each of which may be substituted, or is hydrogen; Z is as defined for Y or is an optionally substituted alkoxy or optionally substituted amino group; R is an organic group; and L is a leaving group. Novel compounds of formula (I) are also disclosed.

Description

HYDROXIMIC ACID DERIVATIVES, PROCESS FOR THEIR PREPARATION AND INTERMEDIATES THEREFOR
This invention relates to processes, intermediates in the processes and compounds obtainable by the processes. Many of the compounds have pesticidal, 5 especially fungicidal, insecticidal and acancidal, activity.
In EP 299 694 there is described the preparation of pesticidal alkyl esters of aryl(methoxyιmιno)acetιc acid. However, the preparation described therein cannot be used to obtain analogous compounds wherein the aryl group is connected to the acetic acid group through an oxygen or sulfur atom.
We have now found a route for preparing such compounds
According to the invention, there is provided a process for preparing a compound of formula I,
Figure imgf000003_0001
(I)
which comprises reacting a compound of formula II
R-X-H (II)
under basic conditions, with a compound of formula III,
Figure imgf000003_0002
(III) wherein;
X is oxygen or sulfur;
Y is alkyl, alkenyl, alkynyl or cycloalkyl, each of which may be substituted, or is hydrogen; Z is as defined for Y or is an optionally substituted alkoxy or optionally substituted ammo group; R is an organic group, preferably an optionally substituted aromatic carbo- or heterocyclyl group; and L is a leaving group, for example halogen, -OSO2Q or -S(0)qQ where Q is an optionally substituted alkyl or optionally substituted carbocyclyl group and q is 1 or 2; preferably L is -SO2Q where Q is C -] -C5 optionally substituted alkyl or optionally substituted phenyl, especially C -1 -C5 alkyl or phenyl.
A variety of basic conditions may be used with the process of the invention. We have found bases such as sodium hydride and potassium carbonate to be particularly effective.
Most compounds of formula III are novel, and therefore the invention includes compounds of formula III with the proviso that when Y is benzyl, L is not -SC>2P
Many compounds of formula I are novel, and therefore the invention includes compounds of general formula la
Figure imgf000004_0001
wherein
X, Y and Z are as defined above; X preferably being oxygen; Y preferably being methyl, cyanomethyl, tπfluoromethyl, difluoromethyl, monofluoromethyl (especially methyl); and Z preferably being methoxy or monomethyiamino, especially monomethyiamino; each R^ , which may be the same or different to any other R^ , is alkyl, alkenyl, alkynyl, or cycloalkyl, each of which may be substituted, or is alkoxy, haloalkoxy, halogen, nitro or cyano; R^ is preferably C-1-C5 alkyl (especially methyl) or halogen (especially chlorine or fluorine); m is 0 to 4, preferably 0 or 1;
R2 IS alkyl, alkenyl, alkynyl, carbocyclyl or heterocyciyl, each of which may be substituted, or is hydrogen or Si(R >3, where R3 IS alkyl, phenyl, alkoxy or haloalkoxy; R2 is preferably optionally substituted phenyl (preferred substituents are C1-C5 alkyl, halogen, haloalkyl or haloalkoxy) or optionally substituted aromatic heterocyciyl (preferred substituents are C1-C alkyl, halogen, haloalkyl, haloalkoxy, optionally substituted phenyl or optionally substituted phenoxy, especially unsubstituted phenyl or halophenyl);
A is a direct bond, -0-, -S(0)n-, -CR4 = CR4-, -C≡C-, -A1-, -A1 -A1-,
-A4-, -A10-, -A1S(0)n-, -OA1-, -S(0)nA1-, -A1-A4-,
-A1 -A4-C(R5) = N-N = CR5-, -A1 -A -C(R5) = N-X2-X3-, -A1-A4-A3-, -A1-A -N(R6)-, -A1-A4-X-CH2-, -A1-A4-A1-, -A1-A -CH2X-, -A1-A4-C(R5) = N-X2-X3-X1-, - A1 -X-C(R5) = N-,
-A1-X-C(R5) = N-N = CR5-, -A1-X-C(R5) = N-N(R6)-, -A1 -X-A2-X1 -, -A1-0-A3-, -A1-0-C(R4) = C(R5)-, -A1 -0-N(R6)-A2-N(R6)-, -A1-0-N(R6)-A2-, -A1-N(R6)-A2-N(R6)-, -A1 -N(R6)-A2- -A1-N(R6)-N = C(R5)-, -A3-A1-, -A -A3-, -A2-NR6-, -A2-0-, -A1-A2-X1-, -A1-A1-A2-X1-, -0-A2-N(R6)-A2-,
-CR4 = CR4-A -X1-, -C≡C-A2-X1-, -N = C(R5)-A2-X1-,
-C(R5) = N-N = C(R5)-, -C(R5) = N-N(R6)- or -(CH2)2-0-N = C(R5)-, where
Figure imgf000005_0001
A2 is -C( = X)-,
A3 is -C(R5) = N-0-,
A4ιs-0-N = C(R5)-,
X1 is 0, S, NR6 or a direct bond, X2 is O, NR6 or a direct bond, X3 is hydrogen, -C( = 0)-, -S02- or a direct bond,
R4, which may be the same or different to any other R4, is alkyl, cycloalkyl or phenyl, each of which may be substituted (preferably by alkyl, phenyl or halogen), or is hydrogen, halogen or cyano; R4 is preferably hydrogen or C-] -C5 alkyl (especially methyl);
R3 , which may be the same or different to any other R°, is alkyl, alkenyl, alkynyl, alkoxy, alkylthio, each of which may be substituted (preferably by halogen), carbo- or hetero-cyclyl which may be substituted (preferably by alkyl or halogen), or is hydrogen; R^ IS preferably hydrogen or C 1 -C5 alkyl (especially methyl);
R°, which may be the same or different to any other R", is optionally substituted alkyl (preferably by halogen) or optionally substituted carbo- or heterocyciyl (preferably by alkyl, phenyl or halogen) , or is hydrogen, or two R^ groups on A, together with the connecting atoms, form a 5 to 7 membered ring; R^ is preferably C 1 -C5 alkyl; where the moiety depicted on the right side of linkage A is attached to R2, or -A-R2 and R 1 together with benzene ring M form an optionally substituted fused ring system.
Preferred linkages A are: a direct bond, -0-, -C≡C-, -A 1 -, -A4-, -A1 0-, -OA 1 -, -A1 -A4- or -A 1 -A4-A3-. Particularly preferred linkages are: a direct bond, -0-, -C≡C-, -A 1 - or -A 1 0-.
It is preferred that when m is 1 , R1 is para to the -A-R2 group.
A preferred group of compounds are those where A is a direct bond, -0-, -C=C-,
-A^ - or -A1 0-, and R2 is phenyl or aromatic heterocyciyl, each of which may be substituted (preferably by C 1 -C5 alkyl, halogen, haloalkyl, haloalkoxy, optionally substituted phenyl or optionally substituted phenoxy). When A is a direct bond R2 is preferably phenyl optionally substituted by C 1 -C5 alkyl, halogen, haloalkyl or haloalkoxy, or R2 is aromatic heterocyciyl (preferably thιazol-2-yl or 1 ,2,4- oxadιazol-3-yl) optionally substituted by C1 -C5 alkyl, halogen, haloalkyl, haloalkoxy or phenyl optionally substituted by halogen. When A is -0-, -C≡C-,
-A1 - or -A10-, R2 is preferably phenyl optionally substituted by C -1 -C5 alkyl, halogen, haloalkyl, haloalkoxy or optionally substituted phenoxy
Any alkyl group present in the molecule may be straight or branched and is preferably of 1 to 1 0 carbon atoms, especially 1 to 7 and particularly 1 to 5 carbon atoms.
Any alkenyl or alkynyl group may be straight or branched and is preferably of 2 to 7 carbon atoms and up to 3 double or triple bonds which may be conjugated, for example vinyl, allyl, butadienyl or propargyl
Any reference to the term carbocyclyl includes saturated carbocyclic groups; unsaturated carbocyclic groups having up to 3 double bonds which may be conjugated; and aromatic carbocyclic groups, e.g. phenyl Carbocyclic groups are typically 3 to 8 membered rings In addition, the term carbocyclyl includes fused carbocyclyl groups, e g napthalene, phenanthrene, indane and indene.
Any reference to the term heterocyciyl includes both aromatic and non-aromatic heterocyciyl groups Heterocyciyl groups are generally 5 6 or 7-membered rings containing up to 4 hetero-atoms selected from nitrogen oxygen and sulfur. Examples of heterocyciyl groups are furyl, thienyl, pyrrolyl, pyrrolinyl, pyrroiidinyl, imidazolyl, dioxolanyl, oxazolyl, thiazolyl, imidazolyl, imidazolinyl, imidazolidinyl, pyrazolyl, pyrazoiinyl, pyrazolidinyl, isoxazolyi, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, pyranyl, pyπdyl, pipeπdinyl, dioxanyi, morpholino, dithianyl, thiomorphoiino, pyπdazinyl, pyπmidinyl, pyrazmyl, piperazinyl, sulfolanyl, tetrazolyl, tπazinyl, azepinyl, oxazepinyl, thiazepinyl, diazepinyl and thiazolmyl. In addition, the term heterocyciyl includes fused heterocyciyl groups, for example benzimidazolyl, benzoxazolyl, imidazopyπdinyl, benzoxazinyl, benzothiazinyl, oxazolopyπdinyl, benzofuranyi, quinolmyl, quinazo nyl, quinoxalinyl, dihydroquinazolinyl, benzothiazolyl, phthalimido, benzofuranyi, benzodiazepinyl, indolyl and isomdolyl Any alkyl, alkenyl, alkynyl, carbocyclyl, heterocyciyl group, alkoxy or alkylthio group when substituted, may be substituted by at least one group, which may be the same or different, and may be selected from the group: nitro, halogen, cyano, acyl, -O-acyl, -S-acyl, optionally substituted ammo, optionally substituted carbocyclyl, optionally substituted heterocyciyl, -SF5, trialkylsilyl, -ORa and -SRa, where Ra is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl and optionally substituted heterocyciyl. Any carbocyclyl or heterocyciyl groups may also be substituted by optionally substituted alkyl, optionally substituted alkenyl and optionally substituted alkynyl
Any ammo group when substituted, may be substituted by one or two optionally substituted alkyl or acyl groups, or two substituents together with the nitrogen to which they are attached may form a heterocyciyl group, preferably a 5 to 7- membered heterocyciyl group, which may be substituted and may contain other hetero atoms, for example morpholino, thiomorpholmo or pipeπdinyl.
The term acyl includes the residue of sulfur and phosphorus-containing acids as well as carboxy c acids. Examples of acyl groups are- -C( = 0)Rb, -C( = 0)ORb, -C( = E)NRbRc, -C( = 0)N(Rb)ORc, -C{ = 0)ONRbRc, -C( = 0)N(Rb)NRcRd,
-C( = 0)SRb, -C( = S)SRb, -S(0)pRb, -S(0)2ORb, -S(0)pNRbRc, -P{ = E)(ORb)(ORc), and -C( = 0)-C( = 0)OR ; where p is 1 or 2; E is 0, S or, where appropriate, NRa or NORa , and where Rb, Rc and R^, which may be the same or different, are as defined for Ra heremabove, or Rb and Rc, or Rc and Rd, together with the atom(s) to which they are attached may form a ring, preferably a 5 to 7- membered heterocyciyl group which may be substituted and may contain other hetero atoms.
In cases where the compounds of the invention exist as the E and Z isomers, the invention includes individual isomers as well as mixtures thereof.
In cases where compounds of the invention exist as tautomeπc isomers, the invention includes individual tautomers as well as mixtures thereof. The compounds of the invention have activity as fungicides, especially against fungal diseases of plants, e.g. mildews and particularly barley powdery mildew (Erysφhe graminis) and vine downy mildew (Plasmopara viticola), rice blast {Pyncularia oryzae), cereal eyespot (Pseudocercosporella herpotnchoides), rice sheath blight [Pe/licu/ana sasakii), grey mould (Botrytis cinerea), damping off {Rhizoctonia solani), wheat brown rust (Puccinia recondita), late tomato or potato blight (Phytophthora infestans), apple scab { Ventuna inaequahs), glume blotch (Leptosphaena nodorum) . Other fungi against which the compounds may be active include other powdery mildews, other rusts, and general pathogens of Deuteromycete, Ascomycete, Phycomycete and Basidomycete origin
The compounds of the invention also have insecticidal, acaπcidal and nematicidal activity and are particularly useful in combating a variety of economically important insects, acarids and plant nematodes, including animal ectoparasites and especially Diptera, such as sheep blow-fly, Lucilia sencata, and house-flies, Musca domestica; Lepidoptera, including Plutella xylostella, Spodoptera littoralis, Heliothis armigera and Piens brassicae, Homoptera, including aphids such as Megoura viciae; Coleoptera, including corn rootworms [Diabrotica spp., e.g. Diabrotica undecimpunctata) , and spider mites, such as Tetranychus spp.
The invention thus also provides a method of combating pests (i.e. fungi, insects, nematodes, acarids and weeds) at a locus infested or liable to be infested therewith, which comprises applying to the locus a compound of formula I
The invention also provides an agricultural composition comprising a compound of formula I in admixture with an agriculturally acceptable diluent or carrier.
The composition of the invention may of course include more than one compound of the invention.
In addition the composition can comprise one or more additional active ingredients, for example compounds known to possess plant-growth regulant, herbicidal, fungicidal, insecticidal or acaπcidal properties. Alternatively the compound of the invention can be used in sequence with the other active ingredient.
The diluent or carrier in the composition of the invention can be a solid or a liquid optionally in association with a surface-active agent, for example a dispersing agent, emulsifying agent or wetting agent. Suitable surface-active agents include anionic compounds such as a carboxylate, for example a metal carboxylate of a long chain fatty acid, an N-acylsarcosinate; mono- or di-esters of phosphoric acid with fatty alcohol ethoxylates or salts of such esters; fatty alcohol sulfates such as sodium dodecyl sulfate, sodium octadecyl sulfate or sodium cetyl sulfate; ethoxylated fatty alcohol sulfates, ethoxylated alkylphenol sulfates, lignm sulfonates, petroleum sulfonates, alkyl-aryl sulfonates such as alkyl-benzene sulfonates or lower alkylnaphthalene sulfonates, e.g. butyl-naphthalene sulfonate, salts of sulfonated naphthalene-formaldehyde condensates, salts of sulfonated phenol-formaldehyde condensates, or more complex sulfonates such as the amide sulfonates, e.g. the sulfonated condensation product of oleic acid and N-methyl tauπne or the dialkyl sulfosuccmates, e.g. the sodium sulfonate of dioctyl succmate Nonionic agents include condensation products of fatty acid esters, fatty alcohols, fatty acid amides or fatty-alkyl- or alkenyl-substituted phenols with ethylene oxide, fatty esters of polyhydπc alcohol ethers, e g sorbitan fatty acid esters, condensation products of such esters with ethylene oxide, e.g polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, acetylenic glycols such as 2,4,7,9-tetramethyl-5-decyne- 4,7-dιol, or ethoxylated acetylenic glycols.
Examples of a cationic surface-active agent include, for instance, an aliphatic mono-, dι-, or polyamine as an acetate, naphthenate or oleate, an oxygen-containing amme such as an amme oxide or polyoxyethylene alkylamme, an amide-linked amme prepared by the condensation of a carboxy c acid with a di- or polyamine; or a quaternary ammonium salt.
The compositions of the invention can take any form known in the art for the formulation of agrochemicals, for example, a solution, a dispersion, an aqueous emulsion, a dusting powder, a seed dressing, a fumigant, a smoke, a dispersible powder, an emulsifiable concentrate or granules. Moreover it can be in a suitable form for direct application or as a concentrate or primary composition which requires dilution with a suitable quantity of water or other diluent before application.
An emulsifiable concentrate comprises a compound of the invention dissolved in a water-immiscibie solvent which is formed into an emulsion with water in the presence of an emulsifying agent.
A dusting powder comprises a compound of the invention intimately mixed and ground with a solid pulverulent diluent, for example, kaolin.
A granular solid comprises a compound of the invention associated with similar diluents to those which may be employed in dusting powders, but the mixture is granulated by known methods. Alternatively it comprises the active ingredient absorbed or adsorbed on a pre-granular diluent, for example, Fuller's earth, attapulgite or limestone grit.
Wettable powders, granules or grains usually comprise the active ingredient in admixture with a suitable surfactant and an inert powder diluent such as china clay
Another suitable concentrate is a flowable suspension concentrate which is formed by grinding the compound with water or other liquid, a wetting agent and a suspending agent.
The concentration of the active ingredient in the composition of the present invention, as applied to plants is preferably within the range of 0.0001 to 1 .0 per cent by weight, especially 0.0001 to 0.01 per cent by weight. In a primary composition, the amount of active ingredient can vary widely and can be, for example, from 5 to 95 per cent by weight of the composition.
In the method of the invention the compound is generally applied to seeds, plants or their habitat Thus, the compound can be applied directly to the soil before, at or after drilling so that the presence of active compound in the soil can control the growth of fungi which may attack seeds. When the soil is treated directly the active compound can be applied in any manner which allows it to be intimately mixed with the soil such as by spraying, by broadcasting a solid form of granules, or by applying the active ingredient at the same time as drilling by inserting it in the same drill as the seeds. A suitable application rate is within the range of from 5 to 1 000 g per hectare, more preferably from 1 0 to 500 g per hectare.
Alternatively the active compound can be applied directly to the plant by, for example, spraying or dusting either at the time when the fungus has begun to appear on the plant or before the appearance of fungus as a protective measure. In both such cases the preferred mode of application is by foliar spraying. It is generally important to obtain good control of fungi in the early stages of plant growth as this is the time when the plant can be most severely damaged. The spray or dust can conveniently contain a pre- or post-emergence herbicide if this is thought necessary. Sometimes, it is practicable to treat the roots of a plant before or during planting, for example, by dipping the roots in a suitable liquid or solid composition. When the active compound is applied directly to the plant a suitable rate of application is from 0.025 to 5 kg per hectare, preferably from 0.05 to 1 kg per hectare.
In addition, the compounds of the invention can be applied to plants or parts thereof which have been genetically modified to exhibit a trait such as fungal, insect and/or herbicidal resistance.
Compounds of the invention may be prepared, in known manner, in a variety of ways.
Compounds of formula III where Z is not an amino group containing a free NH, may be prepared according to reaction Scheme 1 , where QSM is a preferably an alkali metal thioalkoxide, and the oxidation is preferably performed using meta- chloroperbenzoic acid or the like. Scheme 1
phosphorus oxydTlorjαe
Y-0-NH2.HCI
Figure imgf000013_0001
Figure imgf000013_0003
(III)
Alternatively, compounds of formula III where Z is not an amino group containing a free NH may be prepared from iminoyl chlorides according to Scheme 2. Where L is a leaving group such as halogen or sulfonate.
Scheme 2
Figure imgf000013_0004
oxidation
Figure imgf000013_0005
Figure imgf000013_0006
(III) In the preferred case where Z is alkoxy, especially methoxy or ethoxy, the iminoyl sulfones III may be prepared according to Scheme 3. Scheme 3
Figure imgf000014_0001
Compounds of formula la may be prepared by reacting compounds of formula IV under basic condition with compounds of formula III according to Scheme 4 Preferred basic conditions comprise an alkali metal hydride in a suitable solvent, such as tetrahydrofuran, or a weak base such as sodium carbonate in a suitable solvent, such as methylethyl ketone Scheme 4
Figure imgf000014_0002
Compounds of formula lb, i.e. compounds of formula la where A comprises a
-CHR4X- group wherein the carbon is attached to benzene ring M, may be prepared according to Scheme 5 Compounds of formula lc are reacted under basic conditions, with R2XH, where R2XH includes alcohols, phenols, thiophenols, mercaptans, oximes, amides, thioamides etc. Preferred basic conditions comprise an alkali metal hydride in a suitable solvent, e.g. tetrahydrofuran Scheme 5
Figure imgf000015_0001
(lc)
Figure imgf000015_0002
(lb)
The groups R^ , R2 and A may be introduced either before or after reaction of IV with III in Scheme 4
Compounds of formula Id, i.e. compounds of formula la where Z is optionally substituted ammo, may be prepared by a number of routes. A preferred route is shown in Scheme 6 and involves reacting compounds of formula le, where Z is optionally substituted alkoxy, with an amme other than a tertiary amme.
Scheme 6
amination
Figure imgf000015_0003
Figure imgf000015_0004
Compounds of formula If, i.e. compounds of formula la where A is a direct bond and R2 is optionally substituted carbocyclyl or optionally substituted heterocyciyl, may be prepared by a variety of routes. A preferred route is shown in Scheme 7 and involves reacting compounds of formula Ig (Q1 is a displaceable group such as iodine, bromine or tπflate) with a boronic acid or boronate ester of formula R2-
B(ORe)2 (Re is hydrogen or alkyl, or the two groups together form a ring, for example -CH2C(Me)2CH2") in the presence of a palladium catalyst according to the well known method of Suzuki. Preferred conditions involve treating Ig, where
Q1 IS iodine, with a boronic acid R -B(OH>2, sodium carbonate, a catalytic amount of palladium catalyst such as tetrakis (trιphenyiphosphιne)palladιum (0) in a two phase system such as toluene, methanol and water at conditions between room temperature and reflux. For compounds If where Z is alkoxy, reactions are preferably performed at room temperature Where Z is ammo, reactions are preferably carried out at reflux. Scheme 7
Figure imgf000016_0001
(ig) (if)
Compounds of formula If may also be prepared according to Scheme 4, whereby the carbocyclic or heterocychc ring R2, linked by a direct bond A to the benzene ring M are assembled first and then coupled with compound III.
Compounds of formula Ih, i.e. compounds of formula la where A is a direct bond and R2 is polyfluoroalkyl, may be prepared by reacting compounds of formula Ig with a polyfluoroalkyl iodide in the presence of a copper catalyst according to
Scheme 8 Preferred conditions involve reacting Ig, where Q2 is iodide, with polyfuororalkyl iodide and copper-bronze in dry dimethyl sulfoxide solvent at 1 30 °C. Scheme 8
Figure imgf000017_0001
Compounds of formula Ij, i.e. compounds of formula la where A is -C≡C-, may be prepared by a variety of routes. A preferred route involves reacting a compound of formula Ig with a terminal acetylene V in the presence of palladium catalyst, a tertiary amme, a tertiary phosphine and a copper salt in an aprotic solvent. Typical conditions are shown in Scheme 9 Scheme 9
Figure imgf000017_0002
(ig) (ij)
Other methods will be apparent to the chemist skilled in the art as will be the methods for preparing starting materials and intermediates.
The following Examples also make apparent various methods of preparing compounds of the invention as well as processes, starting materials and intermediates of the invention. Structures of isolated novel compounds were confirmed by elemental and/or other appropriate analyses. Where ' H N.M.R. spectra were used to confirm chemical structure, these were performed in CDCI3. Example 1
Methyl 2-(2-chloro-5-methylphenoxy)-2-(methoxyιmιno)acetate (Compound 22) Sodium hydride (8.4 g of a 60% suspension in mineral oil) was added in small portions to a solution containing 2-chloro-5-methyl-phenol (27.3 g) in dry THF (300 ml) keeping the temperature below 20 °C. After stirring for 10 mins, a solution containing the product from stage d) below (37.37 g) in dry tetrahydrofuran (200 ml) was added slowly over 30 mins whilst keeping the temperature below l O °C. When addition was complete, the reaction was allowed to warm to room temperature and stirred for 5 days The solvent was removed in vacuo and the residue partitioned between water and dichloromethane The aqueous phase was extracted with dichloromethane (x3) and the combined organic phases were dried (MgSO^.) and evaporated to give an oily solid which was triturated with di-isopropyl ether to give the title product, m.p. 1 1 8-20 °C
Preparation of starting materials a) Methyl methoxyaminoglyoxyiate
Methoxyl amme hydrochloπde (20 g) was suspended in dichloromethane ( 1 50 ml) . Tπethylamine (25 g) was added and the mixture stirred for 20 mins at room temperature. Methyl oxalyl chloride (30 g) was then added dropwise whilst maintaining the temperature between 20-25 °C. The mixture was stirred for 2 hours at room temperature. Tπethylamine (25 g) was then added dropwise over 20 mins, and the solution stirred for a further 20 mins. The solvent was removed in vacuo, and the residue triturated with ether. The mixture was filtered to remove the solid tπethylamine hydrochloπde and the filtrate was evaporated to give the title product, 1 H N.M.R. 3.78 (3H, s, OMe) and 3.85 (3H, s, OMe) .
b) Methyl 2-chioro-2-(methoxyιmιno)acetate. A solution containing the product from stage a) (5.8 g) and phosphorus oxychloπde (20 ml) were heated under reflux for 1 8 hours. The solution was cooled and excess phosphorus oxychloπde was removed in vacuo. Water was added and the reaction mixture was extracted with dichloromethane The combined organic extracts were dried (MgS04), filtered and the filtrate evaporated to give the title product, m.p. 44-5 °C.
c) Methyl 2-(methoxyιmιno)-2-(methylthιo)acetate. Sodium thiomethoxide (2.5 g) was suspended in dry tetrahydrofuran (20 ml) and a solution containing the product from stage b) below (5.0 g) in dry tetrahydrofuran ( 1 0 ml) was added dropwise The mixture was heated under reflux for 3 hours. On cooling the reaction mixture was poured into water. The reaction mixture was extracted with diethyl ether to give the title product, 1 H N.M.R. 2 38 (3H, s, SMe) , 3 88 (3H, s, OMe) and 4.04
(3H, s, OMe)
d) Methyl 2-(methoxyιmιno)-2-(methylsulfony I) acetate
To a solution containing the product from stage c) below (4 0 g) in dry dichloromethane (40 ml) was added dropwise, a solution containing 55 % meta-chloroperbenzoic acid (8 5 g) in dry dichloromethane (40 ml) . The solution was allowed to stir at room temperature overnight. The reaction mixture was filtered and the filtrate washed sequentially with saturated sodium bicarbonate solution, sodium bisulfite solution and brine, and then dried (MgSO^ The solvent was evaporated to give the title product, m.p.
57-8 °C.
Example 2
Methyl 2-(5-bromomethyl-2-chlorophenoxy)-2-(methoxyιmιno)acetate (Compound 48)
A solution containing the product from Example 1 (2.6 g), 1 ,3-dιbromo-5,5- dimethyl hydantoin (2.9 g) and benzoyl peroxide (0.1 g) in isopropyl acetate (50 ml) was slowly heated to 85 °C. During heating, the reaction mixture darkened and then turned clear as the reaction began. The reaction mixture was heated for 30 mins at 85 °C. On cooling the solvent was removed in vacuo and the residue dissolved in dnsopropyl ether. The mixture was filtered to remove the insoluble dimethyl hydantoin, and the filtrate was purified by silica gel chromatography, gradient eluting with hexane/ ethyl acetate to give the title product, m.p. 65-7 °C. Example 3
Methyl 2-[2-chloro-5-(4-chlorophenoxymethyl)phenoxy]-2-(methoxyιmιno)acetate (Compound 5)
To a solution of the product from Example 2 ( 1 .0 g) and 4-chlorophenol (0.38 g) in acetone was added potassium carbonate (0.3 g) and the mixture was stirred at room temperature for 48 hours. Water was added and the mixture was extracted with ethyl acetate. The combined organic extracts were dried (MgS04>, filtered and evaporated to give a residue which was purified using silica gel chromatography gradient eluting with hexane/ ethyl acetate to give the title product, m.p. 1 1 7-9 °C
Example 4
Λ -Methyl 2-[2-chloro-5-(4-chlorophenoxymethyl)phenoxy]-2- (methoxyιmιno)acetamιde (Compound 9) To a solution of the product from Example 3 (0.24 g) in tetrahydrofuran (2 ml) was added 33% w/v methylamme in ethanol (2 ml), and the solution was stirred at room temperature for 1 8 hours The solvent was removed in-vacuo to give the title product, m.p. 1 26-7 °C
Example 5
Methyl 2-[5-(3-bιphenylyl)-2-methylphenoxy)-2-(methoxyιmιno)acetate (Compound 1 57)
To a solution containing the starting material (see below, 1 .0 g) and 3- biphenylylboronic acid (0.57 g) in toluene (9 ml) and methanol (3 ml) was added sodium carbonate (0.86 g) in water (4 ml) followed by tetrakιs(trιphenylphosphιne) palladium (0) (0.1 7 g). The mixture was heated to 60°C for 2 hours. The mixture was cooled, filtered through kieselguhr and the filtrate poured into brine. The mixture was extracted with toluene (x3) and the combined extracts were dried (MgSθ > and evaporated to give a residue which was purified by silica gel chromatography eluting with 8% ethyl acetate in light petroleum (b.p. 40-60 °C) to give the title product, m.p.1 04-10°C. Preparation of starting materials
Methyl 2-(5-ιodo-2-methylphenoxy)-2-(rnethoxyιmιno) acetate
A mixture containing 5-ιodo-2-methyiphenol (W096 32399), methyl 2-
(methoxyιmιno)-2-(methylsulfonyl)acetate (0.82 g, see Example 1 , stage d) and ground potassium carbonate (0.6 g) in dry methylethyl ketone (28 ml) was heated under gentle reflux with stirring for 3.5 hours. The reaction mixture was cooled, filtered to remove inorganic solids and the filtrate evaporated to dryness in vacuo.
The product was dissolved in dichloromethane, washed with brine and dried
(MgSθ4> . Work-up gave the title product as a solid, m.p. 88-91 °C.
Example 6
Methyl 2- (methoxyιmιno)-2-(2-methyl-5-perfluorobutylphenoxy) acetate
(Compound 1 61 )
A mixture containing methyl -2-(5-ιodo-2-methylphenoxy)-2-(methoxyιmιno) acetate (0 5 g, starting material from Example 5) , perfluorobutyl iodide (0.36 ml) , and copper-bronze powder (0.51 g) in dry dimethyl sulf oxide (2 ml) was heated to 1 30 °C under nitrogen for one hour. On cooling, the reaction mixture was poured onto water and then filtered through kieselguhr, washing through with diethyl ether. The filtrate was extracted with diethyl ether (x3) and the combined ether extracts were washed with brine and dried (MgS04) . Work-up gave a crude product which was purified by silica gel chromatograph eluting with 6% ethyl acetate in light petroleum (b.p. 40-60°C) to give the title product, 1 H N.M.R r5(ppm) 2.40 (3H, s, CH3-Ar), 3.82 (3H, s, CH30), 4.02 (3H, s, CH3ON), 6.86
(1 H, s, Ar-H), 7.25 ( 1 H, d, Ar-H), 7.34 (1 H, d, Ar-H).
Example 7
Λ/-Methyl 2-[5-(3-formylphenyl)-2-methylphenoxy]-2-(methoxyιmιno)acetamιde
(Compound 1 66)
To a solution containing the starting material (0.5 g, see below), 3-formylphenyl boronic acid (0.22 g) in toluene (45 ml) and methanol (3 ml) was added sodium carbonate (0.43 g) in water (3 ml) and tetrakιs(trιphenylphosphine) palladium (0)
(0.085 g) . The reaction mixture was heated to a gentle reflux for 4.5 hours. The reaction mixture was cooled, filtered, and the filtrate extracted ethyl acetate (x3). The combined organic extracts were washed with brine and dried (MgSO4).
Work-up gave a crude product which was purified by silica gel chromatogrphay eluting with 30% ethyl acetate in light petroleum (b.p. 40-60°C) to give the title product as a solid, m.p. 1 28- 1 30 °C (with decomposition)
Preparation of starting materials
Λ/-Methyl 2-(5-iodo-2-methylphenoxy]-2-(methoxyimino)acetamide
The compound was prepared from methyl 2-(5-iodo-2-methylphenoxy]-2-
(methoxyimino)acetate (see Example 5) using conditions analogous to Example 4.
Example 8
Methyl 2-(methoxyimino)-2-[2-methyl-5-(3,4-xylyloxy)phenoxy] acetate
(Compound 1 68)
To a solution containing 2-methyl-5-(3,4-xylyloxy)phenol (0.36 g) in dimethylformamide (4 ml) was added sodium hydride (0.068 g, 60% in mineral oil) . When the effervescence had ceased methyl 2-(methoxyimino)-2- (methylsulphonyl) acetate (0.42 g, the product from Example 1 stage a)) was added and the solution stirred at room temperature for 3.5 hours. The reaction mixture was poured onto water and extracted with diethyl ether (x2) . The combined ether extracts were washed with brine and dried (MgS04> . Work-up gave a crude product which was purified by silica gel chromatography eluting with dichloromethane; light petroleum (b.p. 40-60°C) (2: 1 ) to give the title product, m.p. 66-9°C.
Example 9
Methyl 2-(methoxyimino)-2-[2-methyl-5-(phenylethynyl)phenoxy]acetate
(Compound 1 43)
To a mixture of methyl 2-(5-iodo-2-methylphenoxy)-2-(methoxyimino)acetate (1 .0 g) in triethylamine (50 ml) was added phenylacetylene (0.33 ml) , copper(l) iodide 30 mg), triphenylphosphine ( 1 5 mg) and PdCl2(PPh3>2 ( 1 5 mg) . The reaction was heated to reflux for 2 hours. On cooling, the reaction was filtered through kieselguhr, washing through with toluene. Evaporation of the filtrate in vacuo gave the title compound, m.p. 1 35-8 °C. Example 1 0
Methyl 2-(methoxyιmιno)-2-{2-methyl-5-[ 1 -(3-trιfluoromethylphenyl)ethylιdene amιnooxymethyi]phenoxy}acetate (Compound 1 50)
To a solution containing 3-trιfluoromethylphenylacetophenone oxime (0 32 g) was dissolved in methyl ethyl ketone (14 ml) To this was added potassium carbonate (0 23 g) followed by the product from stage d (see below) (0 5 g) The mixture was heated under gentle reflux for 18 hours On cooling, the mixture was filtered and evaporated to dryness to give a crude product which was purified by silica gel chromatography gradient eluting with ethyl acetate/light petroleum (b p 40-60°C) (5- 20%) to give the title product as a solid, m p 62-4°C
Preparation of Starting Materials a) 3-Hydroxy-4-methyibenzyl acetate
A suspension containing 5-(hydroxymethyl)-2-methylphenol (0 5 g) and Candida Rugosa Lipase Type VII (0 70 g, ex-Sigma) in vinyl acetate ( 14 ml) and hexane (28 ml) was stirred for 4 hours Removal of the enzyme by filtration followed by evaporation in-vacuo gave the title compound which was used without further purification
b) Methyl 2-[5-acetoxymethyl-2-methylphenoxy]-2-(methoxyιmιno)acetate
To a solution containing the product from stage a) ( 10 g) in dry tetrahydrofuran (275 ml) was added sodium hydride (60% in mineral oil, 2 4 g) portionwise over 10 minutes When the effervescence had ceased methyl 2-(methoxyιmιno)-2-(methylsulphonyl) acetate ( 1 1 .9 g, the product from Example 1 stage a) was added portionwise and stirred at room temperature for 1 8 hours. The reaction was quenched with methanol (5 ml), poured onto ice water ( 1 litre) and extracted with diethyl ether The combined organic extracts were washed with brine and dried (MgSθ4)
Work-up gave a crude product which was purified by silica gel chromatography gradient eluting with ethyl acetate: light petroleum (b.p
40-60°C ( 1 -10%) to give the title product Methyl 2-[5-(hydroxymethyl)-2-methylphenoxy]-2-(methoxyimino)acetate A mixture containing the product from stage b) (7.69 g) and potassium carbonate (3.59 g) in dry methanol ( 1 52 ml) was stirred at room temperature for 25 minutes. The mixture was poured into a vigorously stirred solution of water (500 ml) and dichloromethane (500 ml). The layers were separated and the aqueous phase extracted with dichloromethane (x2) . The combined organic extracts were washed with brine and dried (MgS04) . Work-up gave the title compound as a solid.
d) Methyl 2-(5-bromomethyl-2-methylphenoxy)-2-(methoxyιmιno)acetate
To a solution containing the product from stage c) (3.55 g) in dry dichloromethane (66 ml) was added triphenylphosphine (4.04 g) . The solution was stirred at room temperature and carbon tetrabromide (5.1 1 g) was added in one portion. The reaction mixture was stirred at room temperature for 1 8 hours. The mixture was then washed with saturated aqueous sodium bicarbonate solution and the layers separated. The aqueous phase was extracted with dichloromethane (x2) and all organic phases were combined, washed with brine and dried (MgS04). Work up followed by silica gel chromatography gradient eluting with ethyl acetate in petrol (b.p. 40-60°C) ( 10-1 5 %) gave the title compound as a solid, m.p. 84-7 °C.
The following compounds of formula If, i.e. compounds of general formula la where X is oxygen, Y is methyl, m is 1 and R1 is para to -A-R2, were prepared by methods analogous to those of the previous Examples. The moiety depicted on the right side of linkage A is attached to R2.
Figure imgf000025_0001
(if)
Figure imgf000025_0002
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Those compounds in the above table which do not have discrete melting points have the following characteristic ^H N.M.R. data in CDCI3.
Compound 11
1H N.M.R. δ(ppm) (mixture of E/Z isomers) 2.48 and 2.56 (3H, 2xs, CH3S), 3.79 and 3.82 (3H, 2xs, CH3O), 3.98 and 4.02 (3H, 2xs, CH3O), 4.20 and 4.32 (2H, 2xs, CH2-Ar), 6.94-7.80 (7H, m, 7xAr-H) and 8.30 (1H, s, Ar-CH).
Compound 14
1H N.M.R. δ(ppm) (mixture of E/Z isomers) 2.48 and 2.58 (3H, 2xs, CH3S), 2.78 and 2.82 (3H, 2xd, NHCH3), 3.90 (3H, 2xs, CH3O), 4.21 and 4.33 (2H, 2 x s, CH?-Ar), 6.60 (1H, br. s, NH), 7.00-7.80 (7H, m, 7xAr-H) and 8.28 (1H, s, Ar- CH).
Compound 18
1H N.M.R. δ(ppm) 2.28 (3H, s, CH3-Ar), 2.44 (3H, s, CH3S), 3.80 (3H, s,
CH3O), 3.98 (3H, s, CH3O), 4.22 (2H, s , CH2-Ar) and 6.74-7.34 (7H, m,
7xAr-H_).
Compound 34
1H N.M.R. δ(ppm) 2.30 (3H, s, CH3-Ar), 2.44 (3H, s, CH3S), 2.84 (3H, d, CH3NH), 3.90 (3H, s, CH3O), 4.20 (2H, s, CH2-Ar), 6.60 (1H, d, CH3NH) and 6.74-7.32 (7H, m, 7xAr-H). Compound 50
1H N.M.R. δ(ppm) 2.25 (3H, s, CH3), 2.80 (3H, d, CH3NH), 3.90 (3H, s,
CH3ON), 5.15 (2H, s, CH20), 6.65 (1H, br. s, CH3NH), 7.00 - 7.90 (7H, m, 7 x
Ar-H).
Compound 51
1H N.M.R. δ(ppm) 2.25 (3H, s, CH3), 2.85 (3H, d, CH3NH), 3.90 (3H, s,
CH3ON), 5.15 (2H, s, CH 0), 6.60 (1H, br. s, CH3NH), 7.00 - 7.60 (7H, m, 7 x
Ar-H).
Compound 52
1 H N.M.R. δ(ppm) (mixture of E/Z isomers) 1.90 - 2.00 (3H, 3 x s, CH3), 2.05 - 2.10 (3H, 3 x s, CH3), 2.85 (3H, d, CH3NH), 3.90 - 3.95 (6H, 4 x s, CH3ON), 5.10 (2H, s, CH20), 6.65 - 6.75 (1H, 2 x br. s, CH3NH), 6.85 - 7.35 (3H, m, 3 xAr-H).
Compound 54
1H N.M.R. δ(ppm) 2.20 (3H, s, CH3), 2.85 (3H, d, CH3NH), 3.95 (3H, s, CH3ON), 5.00 (2H, s, CH20), 6.70 (1H, br. s, CH3NH), 6.85 - 6.95 (2H, m, 2 x Ar-H), 7.20 - 7.40 (6H, m, Ar-H).
Compound 55
1H N.M.R. δ(ppm) (mixture of E/Z isomers) 2.20 - 2.25 (3H, 2 x s, CH3), 2.85 (3H, d, CH3NH), 3.90 - 4.00 (6H, 4 x s, CH3ON), 5.00 - 5.10 (2H, 2 x s, CH20), 6.70 (1H, br. s., CH3NH), 6.90 - 7.45 (7H, m, 7 x Ar-H).
Compound 69 H N.M.R. δ(ppm) 2.27 (3H, s, CH3), 2.83 (3H, d, CH3NH), 3.90 (3H, s, CH3ON), 4.98 (2H, s, CH20), 6.62 (1H, br. s, CH3NH), 6.84 - 7.90 (8H, m, 8 x Ar-H). Compound 89
1H N.M.R. δ(ppm) (mixture of E/Z isomers) 2.20 (3H, 2 x s, N = C-CH3>, 2.35
(3H, s, CH3), 2.80 - 2.90 (3H, 2 x d, CH3N), 3.95 (3H, 2 x s, CH30), 5.10 (2H, s, CH20), 6.60 (1 H, br.s., NH), 6.75 - 7.60 (7H, m, 7 x Ar-H).
Compound 95
1H N.M.R. δ(ppm) 2.25 (3H, s, N = C-CH3), 2.35 (3H, s, CH3), 2.800 (3H, d,
CH3N), 3.90 (3H, s, CH3O), 5.15 (2H, s, CH20), 6.60 (1H, br.s., NH), 6.75 -
7.90 (7H, m, 7 x Ar-H).
Compound 105
1H N.M.R. δ(ppm) 2.41 (3H, s, CH3-Ar), 2.89 (3H, d, CH3NH), 3.93 (3H, s, CH3ON), 6.64 (1H, br. s, CH3NH), 6.85 (1H, s, Ar-H), 7.22 (1H, d, Ar-H), 7.32(1H, d, Ar-H).
Compound 121
1H N.M.R. δ(ppm) 3.80 (3H, s, CH3O), 4.01 (3H, s, CH3ON), 4.98 (2H, s,
CH20), 6.58 - 7.36 (8H, m, 8 x Ar-H).
Compound 124
1H N.M.R. δ(ppm) (mixture of E/Z isomers) 2.50 and 2.59 (3H, 2 x s, CH3S), 3.83 and 3.84 (3H, 2 x s, CH3O), 4.04 and 4.05 (3H, 2 x s, CH3ON), 4.28 and 4.38 (2H, 2 x s, CH2-Ar), 6.86 - 7.85 (8H, m, 8 x Ar-H), 8.34 and 8.36 (1H, 2 x s, CH = N).
Compound 135
1H N.M.R. δ(ppm) (mixture of E/Z isomers) 2.35 (3H, s, Ar-CH3), 2.50 - 2.60 (3H, 2 x s, CH3S), 3.90 (3H, 2 x s, CH3O), 4.00 (3H, 2 x s, CH3O), 4.25 - 4.35 (2H, 2 x s, CH2S), 6.75 - 8.10 (7H, m, 7 x Ar-H), 8.40 (1H, 2 x s, N = CH). Compound 136
1H N.M.R. δ(ppm) (mixture of E/Z isomers) 2.35 (3H, s, Ar-CH3), 2.50 - 2.60 (3H, 2 x s, CH3S), 3.80 (3H, 2 x s, CH30), 4.00 (3H, 2 x s, CH3O), 4.20 - 4.30 (2H, 2 x s, CH2S), 6.75 - 7.85 (7H, m, 7 x Ar-H), 8.35 (1H, 2 x s, N = CH).
Compound 137
1H N.M.R. δ(ppm) (mixture of E/Z isomers) 2.35 (6H, s, Ar-CH3), 2.45 (3H, br.s, CH3S), 3.75 - 3.85 (3H, 2 x s, CH3O), 4.00 - 4.10 (3H, 2 x s, CH3O), 4.25 (2H, br. s, CH2S), 6.75 - 7.20 (7H, m, 7 x Ar-H).
Compound 141
1H N.M.R. δ(ppm) 2.20 (3H, s, N = C-CH3), 2.30 (3H, s, CH3), 3.70 (3H, s,
CH3O), 4.00 (3H, s, CH3O), 5.10 (2H, s, CH20), 6.70 - 7.60 (7H, m, 7 x Ar-H).
Compound 161
1H N.M.R. δ(ppm) 2.40 (3H, s, CH3-Ar), 3.82 (3H, s, CH3O), 4.02 (3H, s,
CH3ON), 6.86 (1H, s, Ar-H), 7.25 (1H, d, Ar-H), 7.34 (1H, d, Ar-H).
Compound 177
1H N.M.R. δ(ppm) 2.35 (3H, s, CH3-Ar), 2.9 (3H, d, NHCH3), 3.9 (3H, s, OCH3), 6.4 (1H, d), 6.6 (1H, broad, NH), 6.7 (1H, dd, Ar-H), 7.05-7.4 (5H, m).
Compound 184 1H N.M.R. δ(ppm) 2.35 (3H, s, CH3-Ar), 3.8 (3H, s, OCH3), 4.0 (3H, s, OCH3), 6.45 (1H, d), 6.6-6.75 (4H, m), 6.95-7.4 (7H, m).
Compound 185 H N.M.R. δ(ppm) 2.35 (3H, s, CH3-Ar), 3.8 (3H, s, OCH3), 4.0 (3H, s, OCH3), 6.4 (1H, d), 6.65 (1H, dd), 6.9-7.4 (10H, m). Compound 186
1H N.M.R. δ(ppm) 2.35 (3H, s, CH3-Ar), 3.8 (3H, s, OCH3), 4.0 (3H, s, OCH3), 6.5 (1H, d), 6.7 (1H, dd), 7.0 (2H, d), 7.19 (1H, d), 7.35 (1H, m), 7.45 (2H, m) 7.55 (4H, m).
Compound 187
1H N.M.R. δ(ppm) 2.35 (3H, s, CH3-Ar), 3.8 (3H, s, OCH3), 4.0 (3H, s, OCH3),
6.4 (1H, d), 6.6 (1H, dd), 6.85-7.05 (4H, m), 7.15 (1H, d).
Compound 189
1H N.M.R. δ(ppm) 2.35 (3H, s, CH3-Ar), 3.8 (3H, s, OCH3), 4.0 (3H, s, OCH3), 6.4 (1H, d), 6.7 (1H, dd), 7.05-7.4 (5H, m).
Compound 190 1H N.M.R. δ(ppm) 2.35 (3H, s, CH3-Ar), 3.8 (3H, s, OCH3), 4.0 (3H, s, OCH3), 6.4 (1H, d), 6.7 (1H, dd), 6.9-7.2 (5H, m).
Compound 192
1H N.M.R. δ(ppm) 2.35 (3H, s, CH3-Ar), 3.8 (3H, s, OCH3), 4.0 (3H, s, OCH3), 6.5 (1H, d), 6.75 (1H, dd), 6.9 (1H, m), 7.15-7.6 (9H, m).
Compound 196
1H N.M.R. δ(ppm) 1.62 (3H, d, Me), 2.38 (3H, s, CH3-Ar), 3.8 (3H, s, OCH3), 4.02 (3H, s, OCH3), 6.08 (1H, q, CHMe), 7.20-7.45 (7H, m, Ar-H) and 7.75 (1H, d, Ar-H).
Compound 197
1H N.M.R. δ(ppm) 1.55 (9H, s, (Me)3C), 2.38 (3H, s, CH3-Ar), 3.8 (3H, s,
OCH3), 4.00 (3H, s, OCH3) and 7.15-7.62 (3H, m, Ar-H). Compound 199
1H N.M.R. δ(ppm) 0.90 (6H, d, (Me)2CH), 1.28 (3H, d, MeCH), 1.37 (1H, m, CH(Me)2), 1-67 (2H, m, -CH2-), 2.40 (3H, s, CH3-Ar), 3.82 (3H, s, OCH3), 4.03 (3H, s, OCH3), 5.18 (1H, m, -CHO-), 7.20-7.37 (2H, m, Ar-H) and 7.69 (1H, d, Ar-H).
Compound 201 H N.M.R. δ(ppm) 1.59 (3H, d, MeCH), 2.38 (3H, s, CH3-Ar), 3.77 (3H, s, OCH3), 3.98 (3H, s, OCH3), 6.00 (1H, q, -CHMe), 7.20-7.39 (2H, m, Ar-_H) and 7.71 (1H, d, Ar-H).
Compound 206
1H N.M.R. δ(ppm) 3.86 (3H, s, CH3OCO), 4.06 (3H, s, CH3ON) and 7.03-7.97 (1 OH, m, Ar-H).
Compound 213
1H N.M.R. δ(ppm) 1.36 (9H, s, Me3C), 2.89 (3H, d, MeNH), 3.95 (3H, s,
CH3ON), 6.66 (1H, b, NH) and 6.86-7.66 (5H, m, Ar-H).
Compound 214
1H N.M.R. δ(ppm) 2.86 (3H, d, MeNH), 3.97 (3H, s, CH3ON) and 6.66-7.20
(13H, m, Ar-H).
Compound 215
1H N.M.R. δ(ppm) 2.18 (3H, s, Me-ring), 2.86 (3H, d, MeNH), 3.96 (3H, s, CH3ON) and 6.58-7.24 (7H, m, Ar-H). Compound 216
1H N.M.R. δ(ppm) 1.63 (3H, d, MeCH), 2.40 (3H, s, CH3-Ar), 2.80 (3H, d, NHMe), 3.91 (3H, s, OCH3), 6.05 (1H, q, CHMe), 6.63 (1H, br q, NH), 7.16- 7.42 (7H, m, Ar-H) and 7.72 (1H, d, Ar-H).
Compound 219
1H N.M.R. δ(ppm) 0.88 (6H, d, Me2CH-), 1.25 (3H, d, MeCH), 1.32 (1H, m, CHMe2), 1.63 (2H, m, -CH2-), 2.38 (3H, s, CH3-Ar), 2.78 (3H, d, NHMe), 3.86 (3H, s, OCH3), 5.14 (1H, m, -CHO-), 6.78 (1H, br q, NH), 7.19 (1H, d, Ar-H), 7.32 (1H, s, Ar-H) and 7.63 (1H, d, Ar-H).
Compound 230
1H N.M.R. δ(ppm) 1.62 (3H, d, MeCH), 2.39 (3H, s, CH3-Ar), 2.83 (3H, d, NHMe), 3.92 (3H, s, OCH3), 6.02 (1H, q, -CHMe), 6.66 (1H, br q, NH), 7.22- 7.42 (6H, m, Ar-H) and 7.71 (1H, d, Ar-H).
Compound 231
1H N.M.R. δ(ppm) 2.86 (3H, d, MeNH), 3.97 (3H, s, CH3ON), 6.69 (1H, b, NH) and 7.03-8.00 (9H, m, Ar-H).
The following compounds of formula Im, i.e. compounds of general formula la where R2 is 4-methoxylphenyl, A is a direct bond, m is 1 , R^ is methyl para to -A-R2, were prepared by methods analogous to those of the previous Examples.
Figure imgf000039_0001
(Im)
Figure imgf000040_0001
Test Examples
Compounds were assessed for activity against one or more of the following:
Phytophthora infestans: late tomato blight
Plasmopara viticola: vine downy mildew Erysiphe graminis f. sp. tritici: wheat powdery mildew
Pyricula a oryzae: rice blast
Leptosphae a nodorum: glume blotch Aqueous solutions or dispersions of the compounds at the desired concentration, including a wetting agent, were applied by spray or by drenching the stem base of the test plants, as appropriate. After a given time, plants or plant parts were inoculated with appropriate test pathogens before or after application of the compounds as appropriate, and kept under controlled environmental 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 are assessed on a score of 1 to 3 where 1 is little or no control, 2 is moderate control and 3 is good to total control. At a concentration of 500 ppm (w/v) or less, the following compounds scored 2 or more against the fungi specified.
Phytophthora infestans
15, 25, 43, 57, 72, 73, 104, 106, 129, 132, 158, 173, 174, 180, 197, 202 and 222.
Plasmopara viticola: 64, 66-72, 78, 82, 88, 94, 104, 114, 120-125, 127, 145, 146, 158, 164, 165, 184, 186, 188, 217 and 222.
Erysiphe graminis f. sp. tritici:
1, 35, 53, 55, 61, 65, 72, 73, 76, 80, 81, 91-94, 96, 98, 101, 103, 104, 106, 127, 129, 149, 150, 152-154, 159, 164, 169, 176, 180, 187, 190, 211, 215, 217, 218, 220-223 and 225-231. Pyricularia oryzae
2, 9, 11, 14, 16-21, 23, 25, 36-40, 47, 62, 65-67, 72-74, 76, 78-82, 88, 96, 98, 103, 105-107, 120, 127, 129, 132, 140, 142, 143, 157, 159, 160, 161, 167, 169, 173-175, 179, 180, 191, 194, 195, 199 and 231.
Leptosphaeria nodorum
12, 23, 31-33, 37, 38, 47, 54, 58, 61, 65, 72, 76, 78, 80-82, 90-94, 101, 102, 104, 106, 110, 111, 116, 117, 129, 132, 137-139, 141, 147, 148, 156, 157, 164, 169, 171, 180, 186, 202, 211, 214-217, 220-222 and 225-229.

Claims

1 A process for preparing a compound of formula I,
Figure imgf000043_0001
0)
which comprises reacting a compound of formula II
R-X-H (II)
under basic conditions, with a compound of formula III,
Figure imgf000043_0002
(III) wherein
X is oxygen or sulfur;
Y is alkyl, alkenyl, alkynyl or cycloalkyl, each of which may be substituted, or is hydrogen;
Z is as defined for Y or is an optionally substituted alkoxy or optionally substituted amino group;
R is an organic group; and
L is a leaving group.
2 A process according to claim 1 wherein the basic conditions comprise sodium hydride or potassium carbonate.
A compound of formula III as defined in claim 1 , with the proviso that when Y is benzyl, L is not -S0 Ph. A compound of general formula la
Figure imgf000044_0001
(la) wherein X, Y and Z are as defined in claim 1 ; each R1 , which may be the same or different to any other R1 , is alkyl, alkenyl, alkynyl or cycloalkyl, each of which may be substituted, or is alkoxy, haloalkoxy, halogen, nitro or cyano; m is 0 to 4; R2 is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyciyl, each of which may be substituted, or is hydrogen or Si(R3>3, where R3 is alkyl, phenyl, alkoxy or haloalkoxy; A is a direct bond, -0-, -S(0)n-, -CR4 = CR4 -, -C≡C-, -A1-,
-A1-A1-, -A4-, -A10-, -A1S(0)n-, -OA1-, -S(0)nA1-,
-A1 -A4-, -A1-A4-C(R5) = N-N = CR5-, -A -A -C(R5) = N-X2-X3-, -A1-A4-A3-, -A1 -A4-N(R6)-, -A1-A4-X-CH2-, -A1-A -A1-, -A -A4-CH2X-, -A1-A -C(R5) = N-X2-X3-X1-, -A1-X-C(R5) = N-, -A1-X-C(R5) = N-N = CR5-, -A1-X-C(R5) = N-N(R6)-, -A1-X-A2-X1-, -A1-0-A3-, -A1-0-C(R4) = C(R5)-, -A1-0-N(R6)-A2-N(R6)-, -A1-0-N(R6)-A2-, -A1 -N(R6)-A2-N(R6)-, -A1 -N(R6)-A2-, -A1-N(R6)-N = C(R5)-, -A3-A1-, -A4-A3-, -A2-NR6-, -A2-0-, -A1-A2-X1-, -A1-A1-A2-X1-, -0-A2-N(R6)-A2-, -CR4 = CR4-A2-X1 -, -C≡C-A2-X1 -,
-N = C(R5)-A2-X1 -, -C(R5) = N-N = C(R5)-,
-C(R5) = N-N(R6)- or -(CH2)2-0-N = C(R5)-, where
Figure imgf000045_0001
A3 is -C(R5) = N-0-,
Figure imgf000045_0002
X 1 is 0, S, NR6 or a direct bond,
X2 is 0, NR6 or a direct bond,
X3 is hydrogen, -C( = 0)-, -SO2- or a direct bond,
R4, which may be the same or different to any other R4, is alkyl, cycloalkyl or phenyl, each of which may be substituted, or is hydrogen, halogen or cyano;
R5, which may be the same or different to any other R^, is alkyl, alkenyl, alkynyl, alkoxy, alkylthio, carbo- or heterocyciyl each of which may be substituted, or is hydrogen; R6, which may be the same or different to any other R^, IS optionally substituted alkyl or optionally substituted carbo- or heterocyciyl, or is hydrogen, or two R^ groups on A, together with the connecting atoms, form a 5 to 7 membered ring; where the moiety depicted on the right side of linkage A is attached to R2; or -A-R2 and R1 together with benzene ring M form an optionally substituted fused ring system.
A compound according to claim 4 wherein X is oxygen.
A compound according to claims 4 or 5 wherein Y is methyl, cyanomethyl, tπfluoromethyl, difluoromethyl or monofluoromethyl. A compound according to any of claims 4 to 6 wherein Z is methoxy or monomethyiamino.
A compound according to any of claims 4 to 7 wherein when m is greater than 0, R1 is C1 -C5 alkyl or halogen.
A compound according to any of claims 4 to 8 wherein m is 0 or 1 .
A compound according to any of claims 4 to 9, wherein R2 is optionally substituted phenyl or optionally substituted aromatic heterocyciyl.
A compound according to claim 10 wherein when R2 is substituted phenyl, substituents are C 1 -C alkyl, halogen, haloalkyl or haloalkoxy.
A compound according to claim 1 0 wherein when R2 is substituted heterocyciyl, substituents are C 1 -C5 alkyl, halogen, haloalkyl, haloalkoxy or optionally substituted phenyl.
A compound according to any of claims 4 to 1 2 wherein A is a direct bond, -0-, -C≡C-, -A1 -, -A4-, -A1 0-, -OA1 -, -A 1 -A4- or -A 1 -A4-A3-.
A compound according to any of claims 4 to 1 2 wherein A is a direct bond, -0-, -C≡C-, -A1 - or -A 1 0-.
A compound according to any of claims 4 to 14 wherein R4 is hydrogen or C1 -C5 alkyl.
A compound according to any of claims 4 to 1 5 wherein R° is hydrogen or C1 -C5 alkyl.
A compound according to any of claims 4 to 1 6 wherein R° is C 1 -C5 alkyl. A compound according to any of claims 4 to 1 7 wherein when m is 1 , R1 is para to the -A-R2 group.
A compound according to any of claims 4 to 9 wherein A is a direct bond, -0-, -C≡C-, -A 1 - or -A 0- and R2 is phenyl or aromatic heterocyciyl, each of which may be substituted by C-1 -C5 alkyl, halogen, haloalkyl, haloalkoxy, optionally substituted phenyl or optionally substituted phenoxy.
A compound according to any of claims 4 to 9 wherein A is a direct bond, and R2 is phenyl optionally substituted by C 1 -C5 alkyl, halogen, haloalkyl or haloalkoxy, or R2 is aromatic heterocyciyl optionally substituted by C -| - C5 alkyl, halogen, haloalkyl, haloalkoxy or phenyl optionally substituted by halogen.
A compound according to claim 20 wherein the aromatic heterocyciyl is either thiazol-2-yl or 1 ,2,4-oxadiazol-3-yl.
A compound according to any of claims 4 to 9 wherein A is -0-, -C≡C-, -A1 - or -A1 0-, and R2 is phenyl optionally substituted by C 1 -C5 alkyl, halogen, haloalkyl, haloalkoxy or optionally substituted phenoxy,
A pesticidal composition comprising compounds as claimed in any of claims 4 to 22 in admixture with an agriculturally acceptable diluent or carrier.
PCT/GB1999/001664 1998-06-20 1999-06-09 Hydroximic acid derivatives, process for their preparation and intermediates therefor WO1999067209A1 (en)

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US8183351B2 (en) 2006-08-17 2012-05-22 Bayer Cropscience Ag Avermectin derivatives
CN108250102A (en) * 2018-02-01 2018-07-06 青岛润农化工有限公司 It is a kind of（E）- 2- methoxyl group imines -2-（O-tolyl）The preparation method of methyl acetate

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DE1806120A1 (en) * 1967-10-31 1969-05-14 Agripat Sa New carbamoyloximes, processes for their production and their use for combating pests
EP0464381A2 (en) * 1990-06-16 1992-01-08 Bayer Ag 2-Methoxyiminocarboxylic acid esters
WO1992003050A1 (en) * 1990-08-16 1992-03-05 E.I. Du Pont De Nemours And Company Fungicidal sulfoneoxime esters
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8183351B2 (en) 2006-08-17 2012-05-22 Bayer Cropscience Ag Avermectin derivatives
CN108250102A (en) * 2018-02-01 2018-07-06 青岛润农化工有限公司 It is a kind of（E）- 2- methoxyl group imines -2-（O-tolyl）The preparation method of methyl acetate
CN108250102B (en) * 2018-02-01 2020-11-10 青岛润农化工有限公司 Preparation method of (E) -2-methoxyimino-2- (o-tolyl) methyl acetate

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