WO1995001973A1 - Derives d'acide 2-oximino-2-thienyl-acetique - Google Patents

Derives d'acide 2-oximino-2-thienyl-acetique Download PDF

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WO1995001973A1
WO1995001973A1 PCT/EP1994/002043 EP9402043W WO9501973A1 WO 1995001973 A1 WO1995001973 A1 WO 1995001973A1 EP 9402043 W EP9402043 W EP 9402043W WO 9501973 A1 WO9501973 A1 WO 9501973A1
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carbon atoms
chain
straight
branched
formula
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PCT/EP1994/002043
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German (de)
English (en)
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Herbert Gayer
Peter Gerdes
Dietmar Kuhnt
Stefan Dutzmann
Heinz-Wilhelm Dehne
Gerd Hänssler
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Bayer Aktiengesellschaft
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Priority to JP7503789A priority Critical patent/JPH08512295A/ja
Priority to EP94919658A priority patent/EP0707578A1/fr
Priority to AU70727/94A priority patent/AU7072794A/en
Publication of WO1995001973A1 publication Critical patent/WO1995001973A1/fr

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    • 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
    • C07D409/12—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 linked by a chain containing hetero atoms as chain links
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/30—Hetero atoms other than halogen
    • C07D333/32—Oxygen atoms

Definitions

  • the invention relates to new 2-oximino-2-thienyl-acetic acid derivatives, several processes for their preparation and their use as pesticides.
  • certain 2-methoxy-acrylic acid esters such as the compound 3-methoxy-2- (6-phenyl-2-pyridylthio) acrylic acid methyl ester or the compound 3-methoxy-2- [N- (6-phenyl- 2-pyridyl) -N-methylamino] acrylic acid methyl ester or the compound 3-methoxy-2- [5- (4-chlorophenyl) -3-pyridyloxy] acrylic acid methyl ester have fungicidal properties (cf., for example, EP 383 117) .
  • the effectiveness of these previously known compounds is not entirely satisfactory in all fields of application, in particular at low application rates and concentrations.
  • Ar represents optionally substituted aryl or heteroaryl
  • R 1 represents alkyl or haloalkyl
  • R 2 and R 3 are each independently of one another hydrogen, halogen, cyano, nitro, alkyl, alkoxy, alkylthio, alkenyl, alkenyloxy, alkynyl, alkynyloxy, haloalkyl, haloalkoxy, haloalkylthio, haloalkenyl, haloalkenyloxy, haloalkynyl, haloalkynyloxy, alkoxycarbonyl, hydroximinoalkyl, alkoximinoalkyl or represent in each case optionally substituted phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy,
  • R 4 represents hydrogen, alkyl, haloalkyl, cycloalkyl or cyano
  • R 5 represents alkyl or haloalkyl
  • R 6 and R 7 each independently represent hydrogen, alkyl, haloalkyl or alkoxy, and n represents 0, 1 or 2.
  • the compounds of the formula (I) can optionally be present as geometric and / or optical isomers or isomer mixtures of different compositions. Both the pure isomers and the isomer mixtures are claimed according to the invention. It was also found that the new 2-oximino-2-thienyl-acetic acid derivatives of the general formula (I)
  • Ar represents optionally substituted aryl or heteroaryl
  • R 1 represents alkyl or haloalkyl
  • R 2 and R 3 independently of one another each represent hydrogen, halogen, cyano, nitro, alkyl, alkoxy, alkylthio, alkenyl, alkenyloxy, alkynyl, alkynyloxy, haloalkyl, haloalkoxy, haloalkylthio, haloalkenyl, haloalkenyloxy, haloalkynyl, haloalkynyloxy, alkoxycarbonyl,
  • Hydroximinoalkyl alkoximinoalkyl or optionally substituted phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy,
  • A represents oxygen, ethene-1,2-diyl, ethyne-1,2-diyl or one of the following groups -CH 2 -O-; -O-CH 2 -, -CH 2 -S (O) n -, -S (O) n -CH 2 -, SO n -, -
  • Z represents a radical of the formula -OR 5 or -NR 6 R 7 , where
  • R 4 represents hydrogen, alkyl, haloalkyl, cycloalkyl or cyano
  • R 5 represents alkyl or haloalkyl and R 6 and R 7 each independently represent hydrogen, alkyl, haloalkyl or alkoxy, and n represents 0, 1 or 2, is obtained if a) a-oxothienyl acetic acid derivatives of the formula (Ila),
  • R 2 , R 3 , Ar, A and Z have the meaning given above,
  • R 2 , R 3 , Ar, A and Z have the meaning given above and
  • R 8 represents alkyl, or mixtures of a-oxothienyl-acetic acid derivatives of the formula (Ila) and their ketals of the formula (Ilb) with hydroxylamines of the formula (III),
  • R 1 has the meaning given above, or with their hydrogen halide adducts, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary or if b) 2-oximino-2- (halogenomethyl-2-thienyl) acetic acid derivatives of the formula (IV),
  • R 1 , R 2 , R 3 and Z have the meaning given above and
  • X represents halogen, with nucleophiles of the formula (V), Ar-A 1 -H (V) in which
  • a and Ar have the meaning given above and if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary or if c) 2-oximino-2-thienyl-acetic acid derivatives of the formula (Ia),
  • the compounds according to the invention can optionally be present as mixtures of various possible isomeric forms, in particular of E and Z isomers. Both the E and the Z isomers as well as any mixtures of these isomers are claimed.
  • the 2-oximino-2-thienyl-acetic acid derivatives of the general formula (I) according to the invention have a considerably better activity against microorganisms which damage the plants compared to the 2-methoxy-acrylic esters known from the prior art, such as the compound 3-methoxy Methyl 2- (6-phenyl-2-pyridylthio) acrylic acid or the compound 3-methoxy-2- [N- (6-phenyl-2-pyridyl) -N-methylamino] -acrylic acid methyl ester or the compound 3 - Methoxy-2- [5- (4-chlorophenyl) -3-pyridyloxy] -acrylic acid methyl ester, which are chemically and / or functionally obvious compounds.
  • the compound 3-methoxy Methyl 2- (6-phenyl-2-pyridylthio) acrylic acid or the compound 3-methoxy-2- [N- (6-phenyl-2-pyridyl) -N-methylamin
  • the 2-oximino-2-thienyl-acetic acid derivatives according to the invention are generally defined by the formula (I).
  • Compounds of formula (I) are preferred in which represents optionally mono- or polysubstituted, identical or differently substituted aryl with 6 to 10 carbon atoms or for optionally mono- or polysubstituted, identically or differently substituted and / or benzo-fused heteroaryl with 2 to 9 carbon atoms and 1 to 5 identical or different heteroatoms, where as Substituents are possible:
  • R 1 represents straight-chain or branched alkyl having 1 to 8 carbon atoms or straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms
  • R 2 and R 3 each independently of one another represent hydrogen, halogen, cyano, nitro, each straight-chain or branched alkyl, alkoxy, alkylthio each having 1 to 6 carbon atoms, each straight-chain or branched alkenyl or alkenyloxy each having 2 to 6 carbon atoms, each straight-chain or branched alkynyl or alkynyloxy each having 2 to 6 carbon atoms, each straight-chain or branched haloalkyl , Haloalkoxy, haloalkylthio each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, each straight-chain or branched haloalkenyl or haloalkenyloxy each having 2 to 6 carbon
  • Haloalkynyloxy each having 2 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, each straight-chain or branched alkoxycarbonyl, hydroximinoalkyl or alkoximinoalkyl each having 1 to 6 carbon atoms in the individual alkyl parts and, moreover, in each case optionally in the phenyl part, single or multiple, identical or different by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms and / or straight-chain or branched alkoxy having 1 to 4 carbon atoms and / or straight chain or branched tes haloalkoxy with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms substituted phenyl, phenoxy, benzyl, benzyloxy, pheny
  • A represents oxygen, ethene-1,2-diyl, ethyne-1,2-diyl or one of the following groups -CH 2 -O-; -O-CH 2 -, -CH 2 -S (O) n -, -SCO) n -CH 2 -, SO n -,
  • Z represents a radical of the formula -OR 5 or -NR 6 R 7 , where
  • R 4 for hydrogen, for straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, for
  • R 5 represents straight-chain or branched alkyl having 1 to 8 carbon atoms or straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms and R 6 and R 7 each independently of one another represent hydrogen, for straight-chain or branched alkyl 1 to 8 carbon atoms, represents straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, or represents straight-chain or branched alkoxy having 1 to 8 carbon atoms, and n represents 0, 1 or 2, especially those 2-Oximino-2-thienyl-acetic acid derivatives of the formula (I) are preferred in which the group Ar-A and the oximinoacetic acid residue in the thiophene ring are adjacent.
  • Ar is aryl for 6 to 10 carbon atoms, which may be monosubstituted to pentasily, identically or differently substituted, or for heteroaryl which is monosubstituted to tetrasubstituted, identically or differently, and / or benzo fused with 2 to 10 atoms 9 carbon atoms and 1 to 3 identical or different which are heteroatoms - in particular nitrogen, oxygen and / or sulfur, the following being suitable as substituents:
  • Haloalkenyl or haloalkenyloxy each having 2 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, each straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulfonyloxy, hydroximinoalkyl or alkoximinoalkyl each having 1 to 4 carbon atoms in the individual alkyl parts, in each case where appropriate mono- or polysubstituted, identical or different, by halogen and / or straight-chain or branched alkyl having 1 to 3 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms, in each case double-linked alkylene or dioxyalkylene each 1 to 4 carbon atoms, cycloalkyl with 3 to 6 carbon atoms, 5 to 7-membere
  • R 1 represents straight-chain or branched alkyl having 1 to 6 carbon atoms or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms,
  • R 2 and R 3 independently of one another each represent hydrogen, halogen, cyano, nitro, each straight-chain or branched alkyl, alkoxy, alkylthio, each having 1 to 4 carbon atoms, each straight-chain or branched alkenyl or alkenyloxy each having 2 to 4 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio each having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, each straight-chain or branched haloalkenyl or haloalkenyloxy each having 2 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, each straight-chain or branched Alkoxycarbonyl, hydroximinoalkyl or alkoximinoalkyl each having 1 to 4 carbon atoms in the individual alkyl parts and, moreover, in each case optionally in the phenyl part, in one to five
  • Z represents a radical of the formula -OR 5 or -NR 6 R 7 , where
  • R 4 for hydrogen, for straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched haloalkyl with 1 to 4 carbons Substance atoms and 1 to 9 identical or different halogen atoms, stands for cycloalkyl with 3 to 7 carbon atoms or for cyano,
  • R 5 represents straight-chain or branched alkyl having 1 to 6 carbon atoms or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms and
  • R 6 and R 7 each independently represent hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms or straight-chain or branched alkoxy having 1 to 6 carbon atoms 6 carbon atoms stand, as well
  • n 0, 1 or 2
  • n 0, 1 or 2
  • 2-oximino-2-thienyl-acetic acid derivatives of the formula (I) in which the group Ar-A and the oximinoacetic acid residue in the thiophene ring are adjacent are adjacent.
  • Ar for phenyl or naphthyl which is optionally monosubstituted to trisubstituted in the same or different ways or for furanyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, pyrazolyl, imidazolyl, oxadiazolyl and in each case monosubstituted to trisubstituted, identically or differently and / or benzo-fused , Thiadiazolyl, triazolyl, pyridyl,
  • R 1 represents straight-chain or branched alkyl having 1 to 4 carbon atoms or haloalkyl having 1 to 2 carbon atoms and 1 to 5 identical or different halogen atoms,
  • R 2 and R 3 are each independently of one another hydrogen, fluorine, chlorine,
  • Z represents a radical of the formula -OR 5 or -NR 6 R 7 , where
  • R 4 represents hydrogen, methyl, ethyl, trifluoromethyl or cyano
  • R 5 for straight-chain or branched alkyl having 1 to 4 carbon atoms such as methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl or for haloalkyl having 1 to 2 carbon atoms and 1 to 5 identical or different halogen atoms
  • R 6 and R 7 independently of one another each represent hydrogen, for straight-chain or branched alkyl having 1 to 4 carbon atoms, such as methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, for haloalkyl 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms or stand for straight-chain or branched alkoxy with 1 to 4 carbon atoms, and
  • n 0, 1 or 2
  • 2-oximino-2-thienyl-acetic acid derivatives of the formula (I) in which the group Ar-A and the oximinoacetic acid residue in the thiophene ring are adjacent
  • radical definitions given above apply both to the end products of the formula (I) and correspondingly to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with one another as desired, that is to say also between the specified ranges of preferred compounds.
  • reaction sequence of process (a) according to the invention can be represented by the following formula :
  • the a-oxothienyl acetic acid derivatives required as starting compounds for carrying out the process according to the invention are generally defined by the formula (Ila).
  • R 2 , R 3 , Ar, A and Z preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the compounds of the formula (I) according to the invention.
  • ⁇ -Oxothienyl acetic acid derivatives of the formula (Ila) are known in some cases or can be obtained in analogy to known processes (cf., for example, EP 243 014), for example by using halomethylthiophenecarboxylic acid esters of the formula (VII),
  • X represents halogen
  • R 9 represents alkyl, initially in a first stage in analogy to carrying out process (b) according to the invention with nucleophiles of the formula (V),
  • R 4 represents alkyl, haloalkyl, cycloalkyl or cyano, optionally in the presence of a diluent such as acetonitrile and optionally in the presence of a reaction auxiliary such as sodium hydride at temperatures between 0 ° C and 100 ° C and then the thiophenecarboxylic acid esters of the formula (VIII ),
  • R 2 , R 3 , Ar and A 1 have the meaning given above, in a subsequent 3rd stage with conventional acid halide formers such as, for example, thionyl chloride, if appropriate in the presence of a diluent such as dichloroethane, at temperatures between 20 ° C and 120 ° C and then the thiophenecarboxylic acid halides of the formula (X) thus obtainable,
  • conventional acid halide formers such as, for example, thionyl chloride, if appropriate in the presence of a diluent such as dichloroethane
  • R 2 , R 3 , Ar and A 1 have the meaning given above and shark represents halogen, in particular chlorine or bromine, in a subsequent 4th stage with sodium cyanide, optionally in the presence of a diluent such as dichloroethane / water and optionally in the presence a reaction auxiliary such as tetrabutylammo reacting nium bromide at temperatures between 0 ° C and 50 ° C and then the 2-oxo-2-thienylacetonitriles of the formula (XI) thus obtainable,
  • R 5 -OH (XII) in which R 5 has the meaning given above optionally in the presence of a diluent such as t-butyl methyl ether and optionally in the presence of a reaction auxiliary such as acetic anhydride at temperatures between 20 ° C and 150 ° C and optionally subsequently the a-oxothienyl acetic acid derivatives of the formula (IIa-1) obtainable in this way,
  • R 2 , R 3 , R 5 , Ar and A 1 have the meaning given above, or their ketals of the formula (IIb-1),
  • R 2 , R 3 , R 5 , Ar and A 1 have the meaning given above, or mixtures of -oxothienyl-acetic acid esters of the formula (IIa-1) and their ketals of the formula (IIb-1) in a subsequent 6.
  • R 2 , R 3 and R 5 have the meaning given above, first in a 1st stage with formic acid orthoesters of the formula (XIV),
  • R 2 , R 3 , R 5 and R 8 have the meaning given above
  • a halogenating agent such as N-bromosuccinimide
  • a diluent such as carbon tetrachloride
  • a reaction auxiliary such as azodiisobutyrodinitrile ( AIBN) at temperatures between 20 ° C and 150 ° C and then the thus obtainable halomethyl ketals of the formula (XVI)
  • R 2 , R 3 , R 5 and R 8 have the meaning given above and
  • Hal represents halogen, in particular chlorine or bromine, in a subsequent third step in analogy to carrying out process (b) according to the invention with nucleophiles of the formula (V),
  • R 4 represents alkyl, haloalkyl, cycloalkyl or cyano, optionally in the presence of a diluent such as acetonitrile and optionally in the presence of a reaction auxiliary such as sodium hydride at temperatures between 0 ° C. and 100 ° C., then the ketals of the formula (XVII) obtainable in this way,
  • R 2 , R 3 , R 5 , R 8 , Ar and A 1 have the meaning given above in a subsequent 4th stage with aqueous acid, such as, for example, hydrochloric acid, if appropriate in the presence of a diluent such as, for example, dichloromethane at temperatures between 20 ° C. and 120 ° C implemented.
  • aqueous acid such as, for example, hydrochloric acid
  • Halomethyl-thiophenecarboxylic acid esters of the formula (VII) are known or can be obtained in analogy to known processes (see, for example, J. Org. Chem. 51, 235 [1986]).
  • 2-oxo-2- (3-methyl-2-thienyl) acetic acid esters of the formula (XIII) are known or can be obtained in analogy to known processes (cf., for example, Org. Prep. Proced. 2, 249-251 [1970]; BE 896054; US 3,622,569 and the preparation examples), for example by reacting the generally known methylthiophenecarboxylic acids with thionyl chloride to give the corresponding acid chlorides; these are in turn reacted with sodium cyanide in a subsequent reaction to give the corresponding a-oxonitriles which are saponified in a conventional manner in a third stage with acids in the presence of an alcohol and are esterified at the same time.
  • Alcohols of the formula (XII) and formic acid orthoesters of the formula (XIV) are generally known compounds of organic chemistry.
  • the following intermediates are not yet known and are also an object of the invention: thiophenecarboxylic acid esters of the formula (VIII), thiophenecarboxylic acids of the formula (IX), thiophenecarboxylic acid halides of the formula (X), 2-oxo-2-thienylacetonitriles of the formula (XI), ketals of the formula (XV), halomethyl ketals of the formula (XVI), ketals of the formula (XVII) and a-oxothienyl acetic acid derivatives of the formula (Ila) and their ketals of the formula (Ilb) with the exception of the compound 2-oxo-2- (3 -phenoxymethyl-2-thie ⁇ .yl) ethyl acetate.
  • Formula (III) provides a general definition of the hydroxylamines further required as starting materials for carrying out process (a) according to the invention.
  • R 1 preferably represents those radicals which have already been mentioned as preferred for these substituents in connection with the description of the compounds of the formula (I) according to the invention.
  • hydroxylamines of the formula (III), like their hydrohalide salts, such as, for example, their hydrochlorides or hydrobromides, are generally known compounds of organic chemistry.
  • Formula (IV) provides a general definition of the 2-oximino-2- (3-halogenomethyl-2-thienyl) acetic acid derivatives required as starting materials for carrying out process (b) according to the invention.
  • R 1 , R 2 , R 3 and Z preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the compounds of the formula (I) according to the invention.
  • X preferably represents halogen, especially chlorine or bromine.
  • the 2-oximino-2- (3-halomethyl-2-thienyl) acetic acid derivatives of the formula (IV) are not yet known and are also an object of the invention. They are obtained if the 2-oximino-2-thienyl-acetic acid derivatives of the formula (Ib) obtainable with the aid of processes (a) or (c) according to the invention,
  • R 1 , R 2 , R 3 , Ar and Z have the meaning given above, with hydrogen halides, such as, for example, hydrogen chloride or hydrogen bromide, if appropriate in the presence of a diluent such as, for example, methanol at temperatures between 0 ° C. and 80 ° C.
  • hydrogen halides such as, for example, hydrogen chloride or hydrogen bromide
  • a diluent such as, for example, methanol at temperatures between 0 ° C. and 80 ° C.
  • the compounds of the formula (IV) can also be reacted by reacting compounds of the formula (XIII) - above - with hydroxylamines of the formula (III) - above - (analogously to process (a)) and then with halogenating agents, e.g. N-chloro- or N-bromosuccinimide can be obtained by customary methods (cf. the preparation examples).
  • halogenating agents e.g. N-chloro- or N-bromosuccinimide
  • Formula (V) provides a general definition of the nucleophiles which are further required as starting materials for carrying out process (b) according to the invention and for synthesizing the precursors of the formula (II).
  • Ar preferably represents those radicals which have already been mentioned as preferred for these substituents in connection with the description of the compounds of the formula (I) according to the invention.
  • the nucleophiles of the formula (V) are generally known compounds of organic chemistry.
  • Formula (Ia) provides a general definition of the 2-oximino-2-thienyl-acetic acid derivatives required as starting materials for carrying out process (c) according to the invention.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and A preferably represent those radicals which have already been associated with the Be the compounds of formula (I) according to the invention were mentioned as preferred for these substituents.
  • the 2-oximino-2-thienyl-acetic acid derivatives of the formula (Ia) are compounds according to the invention and can be obtained with the aid of processes (a) and (b) according to the invention.
  • Formula (VI) provides a general definition of the amines which are further required as starting materials for carrying out process (c) according to the invention.
  • R 10 and R 11 preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the compounds of the formula (I) according to the invention.
  • the amines of the formula (VI) are generally known compounds of organic chemistry.
  • Inert organic solvents are suitable as diluents for carrying out process (a) according to the invention.
  • These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Nitriles such as acetonitrile, propionitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide;
  • Process (a) according to the invention is preferably carried out in the presence of a suitable reaction auxiliary.
  • All conventional inorganic or organic bases are suitable as such. These include, for example, alkaline earth or Alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or bicarbonates, such as sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate , Sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DA
  • Process (a) according to the invention is usually carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.
  • reaction auxiliaries generally 1.0 to 3.0 mol, preferably 1.0 to 2.0 mol, of hydroxylamine of the formula (1) are employed per mol of a-oxothienyl acetic acid derivative of the formula (II) III) or a corresponding hydrohalide and optionally 1.0 to 6.0 mol, preferably 1.0 to 3.0 mol, of reaction auxiliaries.
  • the reaction is carried out, worked up and isolated by known processes.
  • Inert organic solvents are suitable as diluents for carrying out process (b) according to the invention.
  • These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones such as acetone, butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl
  • the process according to the invention (b) can also be carried out in a two-phase system, such as, for example, water / toluene or water / dichloromethane, if appropriate in the presence of a suitable phase transfer catalyst.
  • suitable phase transfer catalysts are: tetrabutylammonium iodide, tetrabutylammomum bromide, tetrabutylammonium chloride, tributyl-methylphosphonium bromide, trimethyl-C 13 / C 15 -alkylammonium chloride, trimethyl-C 13 / C 15 -alkylammonium bromide, dibenzyl-dimethyl- 12 -ammonium / ammonium-bromide 14- alkyl-benzylammonium chloride, dimethyl-C 12 / C 14 -alkyl-benzylammonium bromide, tetrabutylammonium hydroxide, triethylbenzyl
  • Process (b) according to the invention is preferably carried out in the presence of a suitable reaction auxiliary.
  • All conventional inorganic or organic bases are suitable as such. These include, for example, alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate , Potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate and also tertiary amines, such as trimethylamine, triethylamine, tribu tylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, NJNf-dimethylaminopyridine, diazabicyclooctan
  • reaction temperatures can be varied within a substantial range when carrying out process (b) according to the invention. In general, temperatures between 0 ° C and + 150 ° C, preferably at temperatures between 20 ° C and + 120 ° C.
  • Process (b) according to the invention is usually carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.
  • process (b) generally 1.0 to 3.0 mol, preferably 1.0, are employed per mole of 2-oximino-2- (3-halogenomethyl-2-thienyl) acetic acid derivative of the formula (IV) to 2.0 moles of nucleophile of the formula (V) and optionally 1.0 to 3.0 moles, preferably 1.0 to 2.0 moles, of reaction auxiliaries.
  • the reaction is carried out, worked up and isolated by known processes.
  • Inert organic solvents are suitable as diluents for carrying out process (c) according to the invention.
  • These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Nitriles such as acetonitrile, propionitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide or
  • Process (c) according to the invention is preferably carried out in the presence of a suitable reaction auxiliary.
  • All conventional inorganic or organic bases are suitable as such. These include, for example, alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethyl, potassium tert-butyl lat, sodium hydroxide, potassium hydroxide, ammonium hydroxide , Sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicycl
  • reaction temperatures can be varied within a substantial range when carrying out process (c) according to the invention. In general, temperatures between -30 ° C and + 150 ° C, preferably at temperatures between -20 ° C and + 120 ° C.
  • Process (c) according to the invention is usually carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.
  • process (c) generally 1.0 to 3.0 mol, preferably 1.0 to 1.5 mol, of amine are used per mole of 2-oximino-2-thienyl-acetic acid derivative of the formula (Ia) Formula (VI) and optionally 0.1 to 3.0 mol, preferably 0.5 to 1.5 mol, of base used as reaction auxiliary.
  • 2-oximino-2-thienyl-acetic acid derivatives of the formula (Ia) used as starting products to produce in an upstream reaction in the reaction vessel and then to implement it further without isolation directly in a so-called “one-pot reaction” according to process (c) according to the invention.
  • the reaction is carried out, worked up and isolated in each case analogously to known processes (see, for example, EP 398 692 and the preparation examples).
  • the end products of the formula (I) are purified using customary methods, for example by column chromatography or by recrystallization.
  • the characterization is carried out using the melting point or, in the case of non-crystallizing compounds, using the refractive index or proton nuclear magnetic resonance spectroscopy ( 1 H-NMR).
  • the active compounds according to the invention have a strong microbicidal action and can be used practically to combat unwanted microorganisms.
  • the active ingredients are suitable for use as crop protection agents, in particular as fungicides.
  • Fungicides in plant protection are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.
  • Pythium species such as, for example, Pythium ultimum
  • Phytophthora species such as, for example, Phytophthora infestans
  • Pseudoperonospora species such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubense; Plasmopara species, such as, for example, Plasmopara viticola;
  • Peronospora species such as, for example, Peronospora pisi or Peronospora brassicae;
  • Erysiphe species such as, for example, Erysiphe graminis
  • Sphaerotheca species such as, for example, Sphaerotheca fuliginea
  • Podosphaera species such as, for example, Podosphaera leucotricha
  • Venturia species such as, for example, Venturia inaequalis
  • Pyrenophora species such as, for example, Pyrenophora teres or Pyrenophora graminea (conidial form: Drechslera, synonym: Helminthosporium);
  • Cochliobolus species such as, for example, Cochliobolus sativus (conidial form: Drechslera, synonym: Helminthosporium);
  • Uromyces species such as, for example, Uromyces appendiculatus
  • Puccinia species such as, for example, Puccinia recondita
  • Tilletia species such as, for example, Tilletia caries
  • Ustilago species such as, for example, Ustilago nuda or Ustilago avenae;
  • Pellicularia species such as, for example, Pellicularia sasakii;
  • Pyricularia species such as, for example, Pyricularia oryzae
  • Fusarium species such as, for example, Fusarium culmorum
  • Botrytis species such as, for example, Botrytis cinerea
  • Septoria species such as, for example, Septoria nodorum
  • Leptosphaeria species such as, for example, Leptosphaeria nodorum
  • Cercospora species such as, for example, Cercospora canescens
  • Alternaria species such as, for example, Alternaria brassicae;
  • Pseudocercosporella species such as, for example, Pseudocercosporella herpotrichoides.
  • the fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases allows treatment of above-ground parts of plants, of propagation stock and seeds and of the soil.
  • the active compounds according to the invention can be used with particularly good success to combat diseases in fruit and vegetable cultivation, such as, for example, against the pathogen of apple scab (Venturia inaequalis) or to combat cereal diseases, for example against the pathogen of powdery mildew (Erysiphe graminis) or against Pathogen of the barley mesh spot disease (Pyrenophora teres) or against the pathogen of the brown fur of the wheat (Leptosphaeria nodorum) or against the pathogen of the barley spot disease of the barley or of the wheat (Cochliobolus sativus) or against Fusarium species or for combating rice diseases such as against the pathogen Rice spot disease (Pyricularia oryzae) can be used.
  • the active compounds according to the invention have good in vitro activity.
  • the active ingredients can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV Cold and warm mist formulations.
  • These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can, for example, also be used as auxiliary solvents.
  • auxiliary solvents include aromatics, such as xylene, toluene, alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes, or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide or dimethyl sulfoxide, and water;
  • Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants such as halogenated hydrocarbon
  • Adhesives such as carboxymethyl cellulose, natural and synthetic, powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins and synthetic phospholipids, can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
  • the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention can also be used in their formulations in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the spectrum of activity or to prevent the development of resistance. In many cases, synergistic effects occur.
  • copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,
  • Mancopper Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol,
  • Probenazole prochloraz, procymidone, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilone,
  • Tebuconazole Tebuconazole, tecloftalam, tecnazen, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol,
  • Triazoxide trichlamide, tricyclazole, tridemorph, triflumizole, triforin, triticonazole,
  • Zineb, Ziram bactericides Zineb, Ziram bactericides:
  • Cadusafos Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chloretoxyfos, Chlorfenvinphos,
  • Chlorfluazuron Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin,
  • Fenamiphos fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb,
  • Fenoxycarb fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil,
  • Methamidophos methidathione, methiocarb, methomyl, metolcarb, milbemectin,
  • Parathion A Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamdon, Phoxim, Pirimicarb, Pirimiphos M,, Primiphos A, Profenofos, Profenophos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothiophos, Prothosincl, Pothophos, Pyrothicos , Pyraclophos, Pyradaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen, Quinalphos,
  • Tebufenozid Tebufenpyrad
  • Tebupirimphos Teflubenzuron
  • Tefluthrin Temephos
  • Terbam Terbufos
  • Tetrachlorvinphos Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomenethriazonium, Triomenethriazonium, Tri
  • the active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by pouring, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume process or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of the plants can also be treated.
  • the active compound concentrations in the use forms can be varied within a substantial range: they are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.
  • active ingredient 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g.
  • active ingredient concentrations 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the site of action.
  • Example IV-3 Stage 1
  • the mixture is poured onto a mixture of 25 ml of concentrated hydrochloric acid and 250 g of ice, the organic phase is separated off, dried over sodium sulfate, concentrated in vacuo and the residue is distilled in a high vacuum.
  • Vacuum and vacuum distill the residue in a water jet Vacuum and vacuum distill the residue in a water jet.
  • Example 23 The compound listed as Example 23 in the table above can be prepared, for example, as follows:
  • Example 24 The compound listed as Example 24 in the above table can be made, for example, as follows:
  • Emulsifier 0.6 part by weight of alkyl aryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • the plants are placed in a greenhouse at a temperature of approx. 25 ° C and a relative humidity of approx. 80% in order to promote the development of mildew pustules.
  • Evaluation is carried out 7 days after the inoculation.
  • the compounds according to Preparation Examples 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 21 show a clear superiority in effectiveness compared to the prior art with an active ingredient concentration of 400 g / ha show an efficiency of 75% at 100%.
  • the compounds (A) and (B) show no effect at the same application rate, the compound (C) shows an efficiency of 34%.
  • Emulsifier 0.6 part by weight of alkyl aryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • the plants are placed in a greenhouse at a temperature of approx. 25 ° C and a relative humidity of approx. 80% in order to promote the development of mildew pustules.
  • Evaluation is carried out 7 days after the inoculation.
  • the compounds according to Preparation Examples 1, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 21 show a clear superiority in effectiveness over the prior art which show an efficiency of 75% to 100% at a rate of 400 g / ha.
  • the compounds (A) and (B) show no effect at the same application rate, the compound (C) shows an efficiency of 16%.
  • Emulsifier 0.3 part by weight of alkyl aryl polyglycol ether
  • a part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
  • the plants are then placed in a greenhouse at 20 ° C. and a relative humidity of approx. 70%.
  • Evaluation is carried out 12 days after the inoculation.
  • Emulsifier 0.6 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • the plants are placed in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80% in order to promote the development of mildew pustules.
  • Evaluation is carried out 7 days after the inoculation.
  • Emulsifier 0.3 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • the plants are then placed in a greenhouse at 20 ° C. and a relative humidity of approx. 70%.
  • Evaluation is carried out 12 days after the inoculation.
  • the compounds according to Preparation Examples 4, 22, 87 and 88 show an efficiency of 100% at an active ingredient concentration of 10 ppm.

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  • 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)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

De nouveaux dérivés d'acide 2-oximino-2-thiényl-acétique répondent à la formule (I), dans laquelle Ar, A, R?1, R2, R3¿ et Z ont la signification donnée dans la description. L'invention concerne également plusieurs procédés de préparation de ces composés, de nouveaux produits intermédiaires utilisés à cet effet et leur utilisation comme pesticides.
PCT/EP1994/002043 1993-07-05 1994-06-22 Derives d'acide 2-oximino-2-thienyl-acetique WO1995001973A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP7503789A JPH08512295A (ja) 1993-07-05 1994-06-22 ２−オキシイミノ−２−チエニル−酢酸誘導体
EP94919658A EP0707578A1 (fr) 1993-07-05 1994-06-22 Derives d'acide 2-oximino-2-thienyl-acetique
AU70727/94A AU7072794A (en) 1993-07-05 1994-06-22 2-oximino-2-thienyl-acetic acid derivatives

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE4322275 1993-07-05
DEP4322275.7 1993-07-05
DEP4405428.9 1994-02-21
DE4405428A DE4405428A1 (de) 1993-07-05 1994-02-21 2-Oximino-2-thienyl-essigsäurederivate

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WO1995001973A1 true WO1995001973A1 (fr) 1995-01-19

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JP (1) JPH08512295A (fr)
AU (1) AU7072794A (fr)
DE (1) DE4405428A1 (fr)
IL (1) IL110170A0 (fr)
TR (1) TR27776A (fr)
WO (1) WO1995001973A1 (fr)
ZW (1) ZW7994A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5763475A (en) * 1994-03-30 1998-06-09 Sumitomo Chemical Co., Ltd. Method of control plant disease
US6096895A (en) * 1995-05-17 2000-08-01 E. I. Du Pont De Nemours And Company Heterocyclic dihydrazole compounds and their use for controlling fungal plant diseases
US10743535B2 (en) 2017-08-18 2020-08-18 H&K Solutions Llc Insecticide for flight-capable pests
US10875849B2 (en) 2019-04-11 2020-12-29 Angion Biomedica Corp. Solid forms of (E)-3-[2-(2-thienyl)vinyl]-1H-pyrazole

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0243014A1 (fr) * 1986-04-17 1987-10-28 Imperial Chemical Industries Plc Fongicides
EP0354571A1 (fr) * 1988-08-12 1990-02-14 BASF Aktiengesellschaft Oxime-éthers, procédé pour leur préparation et fongicides les contenant
EP0363818A1 (fr) * 1988-10-14 1990-04-18 BASF Aktiengesellschaft Dérivés d'oximéther, leur procédé de préparation et fongicides les contenant
EP0579071A2 (fr) * 1992-07-16 1994-01-19 BASF Aktiengesellschaft Composés hétéroaromatiques et agents phytosanitaires les contenant

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0243014A1 (fr) * 1986-04-17 1987-10-28 Imperial Chemical Industries Plc Fongicides
EP0354571A1 (fr) * 1988-08-12 1990-02-14 BASF Aktiengesellschaft Oxime-éthers, procédé pour leur préparation et fongicides les contenant
EP0363818A1 (fr) * 1988-10-14 1990-04-18 BASF Aktiengesellschaft Dérivés d'oximéther, leur procédé de préparation et fongicides les contenant
EP0579071A2 (fr) * 1992-07-16 1994-01-19 BASF Aktiengesellschaft Composés hétéroaromatiques et agents phytosanitaires les contenant

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5763475A (en) * 1994-03-30 1998-06-09 Sumitomo Chemical Co., Ltd. Method of control plant disease
US5869687A (en) * 1994-03-30 1999-02-09 Sumitomo Chemical Company, Limited Plant disease-controlling agent
US6096895A (en) * 1995-05-17 2000-08-01 E. I. Du Pont De Nemours And Company Heterocyclic dihydrazole compounds and their use for controlling fungal plant diseases
US10743535B2 (en) 2017-08-18 2020-08-18 H&K Solutions Llc Insecticide for flight-capable pests
US10875849B2 (en) 2019-04-11 2020-12-29 Angion Biomedica Corp. Solid forms of (E)-3-[2-(2-thienyl)vinyl]-1H-pyrazole
US11370783B2 (en) 2019-04-11 2022-06-28 Angion Biomedica Corp. Solid forms of (E)-3-[2-(2-thienyl)vinyl]-1H-pyrazole

Also Published As

Publication number Publication date
JPH08512295A (ja) 1996-12-24
TR27776A (tr) 1995-08-09
ZW7994A1 (en) 1994-09-28
DE4405428A1 (de) 1995-03-30
IL110170A0 (en) 1994-10-07
EP0707578A1 (fr) 1996-04-24
AU7072794A (en) 1995-02-06

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