EP0970061A1 - Derives de dioxazine d'alcoximinomethyle a action fungicide - Google Patents

Derives de dioxazine d'alcoximinomethyle a action fungicide

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Publication number
EP0970061A1
EP0970061A1 EP98912428A EP98912428A EP0970061A1 EP 0970061 A1 EP0970061 A1 EP 0970061A1 EP 98912428 A EP98912428 A EP 98912428A EP 98912428 A EP98912428 A EP 98912428A EP 0970061 A1 EP0970061 A1 EP 0970061A1
Authority
EP
European Patent Office
Prior art keywords
methyl
carbon atoms
trifluoromethyl
ethyl
propyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98912428A
Other languages
German (de)
English (en)
Inventor
Peter Gerdes
Herbert Gayer
Bernd-Wieland Krüger
Ulrich Heinemann
Bernd Gallenkamp
Ralf Tiemann
Stefan Dutzmann
Karl-Heinz Kuck
Klaus Stenzel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
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Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0970061A1 publication Critical patent/EP0970061A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D273/00—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00
    • 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
    • A01N43/88—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 six-membered rings with three ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/36—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atoms of the oxyimino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/40—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atoms of the oxyimino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
    • 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
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D307/81—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the invention relates to new alkoximinomethyldioxazine derivatives, a process for their preparation and their use as fungicides, as well as new intermediates and several processes for their production.
  • R ⁇ represents optionally substituted alkyl or cycloalkyl
  • Rl represents hydrogen, cyano or in each case optionally substituted alkyl or cycloalkyl
  • R ⁇ represents hydrogen or in each case optionally substituted alkyl or cycloalkyl
  • Z represents optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl or heterocyclyl and
  • E ⁇ , ⁇ ? -, ⁇ ? and E ⁇ are the same or different and each independently represent hydrogen, alkyl, haloalkyl or hydroxyalkyl, or
  • i, 1? -, L? and i are the same or different and each independently represent hydrogen, halogen, cyano, nitro, each optionally substituted by halogen substituted alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl.
  • the saturated or unsaturated hydrocarbon chains such as alkyl, alkanediyl, alkenyl or alkynyl
  • the saturated or unsaturated hydrocarbon chains are in each case straight-chain or branched, also in combination with heteroatoms, such as in alkoxy, alkylthio or alkylamino. If an alkyl or alkanediyl chain is interrupted by more than one heteroatom, these can be the same or different. If an alkyl or alkanediyl chain is interrupted by more than one oxygen atom, two oxygen atoms are not directly adjacent.
  • Halogen generally represents fluorine, chlorine, bromine or iodine, as well as
  • Pseudohalogens such as, for example, cyano, preferably for fluorine, chlorine, bromine or cyano, in particular for fluorine or chlorine.
  • Aryl stands for aromatic, mono or polycyclic hydrocarbon rings, e.g. Phenyl, naphthyl, anthranyl, phenanthryl, preferably phenyl or naphthyl, especially phenyl.
  • Heterocyclyl stands for saturated or unsaturated, as well as aromatic, ring-shaped compounds in which at least one ring member is a hetero atom, ie an atom other than carbon. If the ring contains several heteroatoms, these can be the same or different. Heteroatoms are preferably oxygen, nitrogen or sulfur. If necessary, the ring-shaped connections form with others carbocyclic or heterocyclic, fused or bridged rings together form a polycychic ring system. Mono- or bicyclic ring systems are preferred, in particular mono- or bicyclic aromatic ring systems.
  • Cycloalkyl stands for saturated, carbocyclic, ring-shaped compounds which optionally form a polycychic ring system with further carbocyclic, fused or bridged rings.
  • X represents halogen, if appropriate in the presence of a diluent and if appropriate in the presence of an acid acceptor.
  • the compounds of the invention can optionally be used as mixtures of various possible isomeric forms, in particular stereoisomers, such as. B. 20
  • E and Z or optical isomers are present. Both the E and the Z isomers, the individual enantiomers, the racemates and any mixtures of these isomers are claimed.
  • the present application preferably relates to alkoximinomethyl-dioxazine derivatives of the formula (I) in which
  • Rl for hydrogen, cyano or optionally with halogen or alkoxy
  • R ⁇ represents hydrogen or alkyl having 1 to 6 carbon atoms optionally substituted by halogen or alkoxy having 1 to 4 carbon atoms or cycloalkyl having 3 to 8 carbon atoms optionally substituted by halogen, alkyl or alkoxy each having 1 to 4 carbon atoms,
  • G for a single bond optionally interrupted by one or two heteroatoms, alkanediyl with 1 to 5 chain links (although the carbon atom to which R * is bound always has a carbon atom of
  • Alkanediyl chain is connected) or a group ' °, in which
  • R represents hydrogen or alkyl, each optionally substituted by halogen or alkoxy having 1 to 4 carbon atoms, having 1 to 6 Carbon atoms, alkenyl having 2 to 6 carbon atoms or alkynyl having 2 to 6 carbon atoms or for cycloalkyl having 3 to 8 carbon atoms optionally substituted by halogen, alkyl or alkoxy each having 1 to 4 carbon atoms or for arylalkyl having 1 to 4 carbon atoms optionally substituted in the aryl part Alkyl part stands, where the substituents are selected from the following list:
  • each straight-chain or branched haloalkenyl or haloalkenyloxy each having 2 to 6 carbon atoms and 1 to 1 1 identical or different halogen atoms
  • each straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulfonyloxy, hydroximinoalkyl or alkoximinoalkyl each having 1 to 6 carbon atoms in the individual alkyl parts each optionally one or more times, identically or differently, 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 the same or different halogen atoms substituted, in each case doubly linked alkylene or dioxyalkylene, each having 1 to 6 carbon atoms,
  • Halogen cyano, hydroxy, amino, Cj-C ⁇ alkoxy, C1-C4-alkylthio, C1-C4-alkylsulfinyl or C1-C4-alkylsulfonyl (which can in each case optionally be substituted by halogen) substituted alkyl having 1 to 8 carbon atoms;
  • alkenyl or alkynyl each optionally substituted by halogen, each having up to 8 carbon atoms; or for phenyl, naphthyl, cycloalkyl or cycloalkenyl, each of which is optionally mono- or polysubstituted in the same or different ways, each having 3 to 8 carbon atoms or for heterocyclyl having 3 to 7 ring members, at least one of which is for oxygen, sulfur or nitrogen and optionally one or two more represents nitrogen, the possible substituents preferably being selected from the following list: halogen, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl;
  • haloalkyl straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfmyl or haloalkylsulfonyl 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 atoms and 1 to 11 identical or different halogen atoms;
  • Heterocyclyl or heterocyclyl-methyl each with 3 to 7 ring members, of which 1 to 3 are identical or different heteroatoms - in particular nitrogen, oxygen and / or sulfur -
  • a ⁇ represents alkyl having 1 to 4 carbon atoms or cycloalkyl having 1 to 6 carbon atoms and
  • a ⁇ is alkyl with 1 to 4 carbon atoms which is optionally substituted by cyano, alkoxy, alkylthio, alkylamino, dialkylamino or phenyl,
  • Alkenyl or alkynyl each having 2 to 4 carbon atoms and
  • E, ⁇ ? -, ⁇ ? and ⁇ ß are the same or different and independently represent hydrogen, alkyl or hydroxyalkyl each having 1 to 4 carbon atoms or haloalkyl having 1 to 4 carbon atoms and 1 to five identical or different halogen atoms, or
  • l2-, l? and are the same or different and each independently represent hydrogen, halogen, cyano, nitro, each optionally substituted by 1 to 5 halogen atoms, alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms.
  • the present application relates in particular to compounds of the formula (I) in which
  • Rl for hydrogen, cyano, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
  • R ⁇ represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, trifluoroethyl, cyclopropyl, cyclobutyl, G for a single bond, methanediyl, 1,1-ethanediyl, 1,2-ethanediyl, 1,1-, 1,2-, 1,3- or 2,2-propanediyl, 1,1-, 1,2-, 1 , 3-, 1,4-, 2,2-, 2,3-butanediyl or 1, 1-, 1,2- or l, 3- (2-methyl-propanediyl), -O-CH2- (where Z is connected to the oxygen atom),
  • Z for each optionally single to triple, identical or different, by chlorine, fluorine, bromine, cyano, hydroxy, amino, methoxy, ethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, trifluoroethoxy - methylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl; for phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclo
  • Al represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl or cyclobutyl and 3
  • E, E 2 , E ⁇ and E ⁇ are the same or different and are independently hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, hydroxymethyl, trifluoromethyl or Trifluorethyl stand, or
  • L, L 2 , L ⁇ and L ⁇ are the same or different and are each independently hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, di-fluorochloromethoxy, trifluoromethylthio, difluoromethylthio, difluoromethylthio, difluoromethylthio, difluoromethyl, difluoromethyl, difluoromethyl, difluoromethyl Trifluoromethylsul
  • the present application also relates in particular to compounds of the formula (I) in which
  • R1 represents hydrogen, cyano, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, trifluoroethyl, cyclopropyl, cyclobutyl,
  • R 2 represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, trifluoroethyl, cyclopropyl, cyclobutyl,
  • allyl, crotonyl, 1-methyl-allyl, propargyl or 1-methyl-propargyl which are optionally monosubstituted to trisubstituted by fluorine or chlorine;
  • Methoxy, ethoxy, phenyl (which may be replaced by fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy is substituted), methyl, ethyl, n- or i-propyl substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl; stands for benzyl, phenyl-1-ethyl or phenyl-2-ethyl which is monosubstituted to trisubstituted in the phenyl part in each case, the possible substituents preferably being selected from the list below:
  • A represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl or cyclobutyl and
  • E, E 2 , E ⁇ and E ⁇ are the same or different and are independently hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, hydroxymethyl, trifluoromethyl or Trifluorethyl stand, or
  • Carbon atoms to which they are attached form a cycloaliphatic ring with five, six or seven carbon atoms and
  • L, L 2 , L ⁇ and Ix are the same or different and are each independently hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, di-fluorochloromethoxy, trifluoromethyl, diflifluoromethyl, diflifluoromethyl, diflifluoromethyl, diflifluoromethyl, difluorifluoromethyl stand.
  • a particularly preferred group of compounds according to the invention are those compounds of the formula (I) in which
  • Rl stands for cyclopropyl or in particular methyl
  • R 2 represents hydrogen
  • G represents a single bond or -O-CH2- (where Z is connected to the oxygen atom),
  • a ⁇ represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl or cyclobutyl and
  • El and E 2 are the same or different and are each independently
  • E ⁇ and E ⁇ stand for hydrogen, Ll and L ⁇ are the same or different and each independently represent methyl or in particular hydrogen and
  • Another particularly preferred group of compounds according to the invention are those compounds of the formula (I) in which
  • Rl stands for cyclopropyl or in particular methyl
  • R 2 represents hydrogen
  • G stands for a grouping N X ° X R3 , in which
  • R ⁇ in particular represents methyl or benzyl which is monosubstituted to trisubstituted by fluorine, chlorine, bromine, cyano, nitro, methyl or methoxy, optionally in the phenyl part,
  • Cyclobutyl, cyclopentyl, cyclohexyl or for 1,2-oxazolyl, benzo appearsanyl or in particular phenyl which is in each case monosubstituted to trisubstituted by identical or different substituents, the possible substituents preferably being selected from the list below:
  • A represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl or cyclobutyl and
  • E ⁇ and E 2 are the same or different and each independently represents methyl or in particular hydrogen
  • eats and? are identical or different and each independently represent methyl or in particular hydrogen and
  • Formula (II) provides a general definition of the 3- (l-hydroxyphenyl-l-alkoximinomethyl) dioxazines required as starting materials for carrying out process a) according to the invention.
  • E *, E 2 , E ⁇ , E ⁇ , iß, L 2 , L ⁇ and iß preferably or in particular have those meanings which are already in connection with the description of the compounds of the formula according to the invention
  • the 3- (l-hydroxyphenyl-l-alkoximinomethyl) dioxazines of the formula (II) are known and can be prepared by known processes (WO 95-04728).
  • Formula (III) provides a general definition of the acrylic acid halides required to carry out process a) according to the invention as starting materials.
  • G, R, R 2 and Z preferably or in particular have those meanings which have already been mentioned as preferred or as particularly preferred for G, Rl in connection with the description of the compounds of the formula (I) according to the invention , R 2 and Z were specified.
  • X represents halogen, preferably chlorine.
  • R, R 2 , R ⁇ , X and Z have the meanings given above.
  • halogenating agent such as thionyl chloride, phosgene, phosphorus pentachloride or phosphorus oxychloride
  • a diluent such as 1,2-dichloroethane
  • Formula (IV) generally defines the acrylic acids required as starting materials for carrying out process b) according to the invention.
  • R, R 2 ,? and Z preferably or in particular those meanings which have already been given in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for R, R 2 , R ⁇ and Z.
  • R 4 represents alkyl
  • a diluent for example an alcohol, such as methanol or ethanol, optionally in a mixture with water, and optionally in the presence of a base, such as sodium hydroxide or
  • Potassium hydroxide or an acid, such as hydrochloric acid or sulfuric acid, hydrolyzed.
  • Formula (V) provides a general definition of the acrylic acid esters required as starting materials for carrying out process c) according to the invention. In this
  • Formula (V) have Rl, R 2 , R? and Z preferably or in particular those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or particularly preferred for R, R 2 , R? and Z were specified.
  • R 4 represents alkyl, preferably methyl or ethyl.
  • the acrylic acid esters of the formula (V) are also the subject of the present application as new substances. They are obtained if (process d) ⁇ -diketone monooximes of the formula (VI)
  • R, R ⁇ and Z have the meanings given above,
  • R 2 and R 4 have the meanings given above and
  • R 5 represents alkyl
  • a diluent for example an ether such as tetrahydrofuran, and optionally in the presence of a base such as
  • Formula (VI) provides a general definition of the ⁇ -diketone monooximes required as starting materials for carrying out process d) according to the invention.
  • R, R and Z preferably or in particular have those
  • ⁇ -diketone monooximes of the formula (VI) are known and / or can be prepared by known methods (compare, for example, Diels; Stern, Chem.Ber., 40 (1907), 1624).
  • alkoxycarbonylmethanephosphonic acid dialkyl esters still required as starting materials for carrying out process d) according to the invention are as follows:
  • R 2 and R 4 preferably or in particular have those meanings which have already been given as preferred or as particularly preferred for R 2 and R 4 in connection with the description of the compounds of the formula (I) according to the invention.
  • R ⁇ is alkyl, preferably methyl or ethyl.
  • alkoxycarbonylmethanephosphonic acid dialkyl esters of the formula (VII) are known synthetic chemicals. 2
  • Suitable diluents for carrying out process a) according to the invention are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Amides such as N, N-di
  • Process a) according to the invention is optionally carried out in the presence of a suitable acid acceptor.
  • a suitable acid acceptor All conventional inorganic or organic bases are suitable as such. These preferably include alkaline earth metal or
  • Tributylamine N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecen (DBU).
  • DABCO diazabicyclooctane
  • DBN diazabicyclonones
  • DBU diazabicycloundecen
  • reaction temperatures can be varied within a substantial range when carrying out process a) according to the invention. In general, temperatures from 0 ° C to 150 ° C, preferably at temperatures from 0 ° C to 80 ° C.
  • the processes according to the invention are generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure - generally between 0.1 bar and 10 bar.
  • the substances according to the invention have a strong microbicidal action and can be used to control unwanted microorganisms, such as fungi and bacteria, in crop protection and in material protection.
  • Fungicides can be used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and
  • Bactericides can be used in crop protection to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
  • Xanthomonas species such as, for example, Xanthomonas campestris pv. Oryzae;
  • Pseudomonas species such as, for example, Pseudomonas syringae pv. Lachrymans;
  • Erwinia species such as, for example, Erwinia amylovora;
  • 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
  • Plasmopara species such as, for example, Plasmopara viticola
  • Bremia species such as, for example, Bremia lactucae
  • Peronospora species such as, for example, Peronospora pisi or P. brassicae; ⁇ L
  • Erysiphe species such as, for example, Erysiphe graminis
  • Sphaerotheca species such as, for example, Sphaerotheca Sportsiginea;
  • 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 P. graminea
  • Drechslera (Conidial form: Drechslera, Syn: Helminthosporium);
  • Cochliobolus species such as, for example, Cochliobolus sativus (conidial form: Drechslera, Syn: Helminthosporium);
  • Uromyces species such as, for example, Uromyces appendiculatus
  • Puccinia species such as, for example, Puccinia recondita
  • Sclerotinia species such as, for example, Sclerotinia sclerotiorum
  • 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; n
  • 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 active compounds according to the invention can be used with particularly good success in combating cereal diseases, for example against Leptosphaeria species, diseases in wine, fruit and vegetable cultivation, for example against Venturia and Plasmopara species, or for rice diseases, for example against Pyricularia species.
  • cereal diseases for example against Leptosphaeria species, diseases in wine, fruit and vegetable cultivation, for example against Venturia and Plasmopara species, or for rice diseases, for example against Pyricularia species.
  • Other cereal diseases such as, for example, Septoria, Pyrenophora or Cochliobolus species, are also successfully combated.
  • the active compounds according to the invention are also suitable for increasing the crop yield. They are also less toxic and have good plant tolerance.
  • the active ingredients can be converted into the 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 -
  • 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, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents Means. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents.
  • extenders that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents Means.
  • surface-active agents that is to say emulsifiers and / or dispersants and / or foam-generating agents Means.
  • organic solvents can, for example, also be used as auxiliary solvents.
  • liquid solvents aromatics, such as xylene, toluene or 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 and 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 hydrocarbons and butane,
  • Solid carriers are: e.g. natural rock meals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock meals, such as highly disperse silica, aluminum oxide and silicates.
  • natural rock meals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth
  • synthetic rock meals such as highly disperse silica, aluminum oxide and silicates.
  • the following are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite,
  • Possible emulsifiers and / or foaming agents are: e.g. nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates.
  • Possible dispersants are: e.g. Lignin liquor and methyl cellulose.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers can be used in the formulations, such as
  • Gum arabic polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, e.g. 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 are used.
  • inorganic pigments e.g. 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 are used.
  • the formulations generally contain between 0.1 and 95 percent by weight
  • Active ingredient preferably between 0.5 and 90%.
  • the active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols,
  • the active compounds according to the invention can also be used 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.
  • fungicides bactericides
  • acaricides nematicides or insecticides
  • synergistic effects are obtained, i.e. the effectiveness of the mixture is greater than the effectiveness of the individual components.
  • Debacarb dichlorophene, diclobutrazole, diclofluanide, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazole
  • Imazalil Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Immamycin, Isoprothiolan,
  • Mancopper Mancozeb, Maneb, Meferimzone, Mepanipyrirri, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Meth tartroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,
  • Tebuconazole Tecloftalam, Tecnazen, Tetcyclacis, Tetraconazole, Thiabendazole, Thicyofen, Thifluzamide, Thiophanate-methyl, Thira, Tioxymid, Tolclofos-methyl, Tolylfluanid,
  • Triadimefon Triadimenol, Triazbutil, Triazoxid, Trichlamid, Tricyclazol, Tridemo ⁇ h, Triflumizol, Triforin, Triticonazol,
  • Bacillus thuringiensis 4-bromo-2- (4-chloro-phenyl) - 1 - (ethoxymethyl) -5- (trifluoromethyl) - 1H-pyrrole-3-carbonitrile, bendiocarb, ben Divisionacarb, bensultap, betacyfluthrin, bifenthrin,
  • BPMC Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxim, Butylpyridaben, Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloethocarb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos, N - [(6- Chloro-3-pyridinyl) -methyl] -N-cyano-N-methyl-ethanimidamide, Chlo ⁇ yrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin,
  • Fenamiphos Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Fluazuron, Flucycloxuron, Flucythrinat, Flufenproxatonophon, Flufenproxaton, Fufenionfonium, Flufenproxofonon, Flufenproxofonon, Furathiocarb,
  • Mecarbam Mevinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathione, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
  • Parathion A Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenophos, Promecarb,
  • Tebufenozide Tebufenpyrad
  • Tebupirimiphos Teflubenzuron
  • Tefluthrin Temephos
  • Terbam Terbufos
  • Tetrachlorvinphos Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomenhriazon, Tralomenhriazon, Tronomenhrononium,
  • 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 application rates can be varied within a relatively wide range, depending on the type of application.
  • the active compound application rates are generally between 0.1 and 10,000 g ha, preferably between 10 and 1,000 g / ha.
  • the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per
  • the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha. Manufacturing examples:
  • Emulsifier 3 parts by weight of alkylaryl polyglycol ether
  • Active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.
  • Emulsifier 3 parts 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 the greenhouse at approx. 21 ° C. and a relative humidity of approx. 90%.
  • Evaluation is carried out 12 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.
  • Example C (1), (4), (5), (6), (7), (8) and (9) with an exemplary active ingredient application rate of 10 g / ha an efficiency of up to 100% compared to the untreated control.
  • Example C
  • 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. 15 ° C and a relative humidity of 80%.
  • Evaluation is carried out 10 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.
  • the following compound of preparation examples (4) shows an efficacy of 70% compared to the untreated control with an exemplary active compound application rate of 25 g / ha. ⁇
  • Emulsifier 0.06 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted to the desired concentration with water and the stated amount of emulsifier.
  • Evaluation is carried out 4 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.
  • the following compounds of preparation examples (3), (7), (8) and (9) show an efficiency of more than 80% in comparison with an exemplary amount of active ingredient applied of 750 g / ha and an exposure time of one day for untreated control.
  • Emulsifier 0.06 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • the plants are then placed in a greenhouse at a temperature of approximately 20 ° C. and a relative atmospheric humidity of 80% in order to promote the development of raw pustules.
  • Evaluation is carried out 10 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

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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)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyridine Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne de nouveaux dérivés de dioxazine d'alcoximinométhyle de la formule (I), un procédé permettant de les préparer et leur utilisation comme fongicides, ainsi que de nouveaux produits intermédiaires et plusieurs procédés permettant de les préparer.
EP98912428A 1997-03-13 1998-03-02 Derives de dioxazine d'alcoximinomethyle a action fungicide Withdrawn EP0970061A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19710355A DE19710355A1 (de) 1997-03-13 1997-03-13 Alkoximinomethyldioxazinderivate
DE19710355 1997-03-13
PCT/EP1998/001165 WO1998040365A1 (fr) 1997-03-13 1998-03-02 Derives de dioxazine d'alcoximinomethyle a action fungicide

Publications (1)

Publication Number Publication Date
EP0970061A1 true EP0970061A1 (fr) 2000-01-12

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EP98912428A Withdrawn EP0970061A1 (fr) 1997-03-13 1998-03-02 Derives de dioxazine d'alcoximinomethyle a action fungicide

Country Status (6)

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US (1) US6281209B1 (fr)
EP (1) EP0970061A1 (fr)
JP (1) JP2001518082A (fr)
AU (1) AU6727098A (fr)
DE (1) DE19710355A1 (fr)
WO (1) WO1998040365A1 (fr)

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DE50000412D1 (de) 1999-01-13 2002-10-02 Basf Ag Azadioxacycloalkene und ihre verwendung zur bekämpfung von schadpilzen und tierischen schädlingen
CN104447337B (zh) * 2014-12-04 2017-01-04 安徽师范大学 一种肉桂酸酯类衍生物及其制备方法

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Publication number Priority date Publication date Assignee Title
EP0080225B1 (fr) 1981-11-23 1985-08-07 Agfa-Gevaert N.V. Méthode pour la préparation de dispersions aqueuses et stables de perles polymériques, ainsi que l'utilisation de ces dispersions dans des éléments photographiques
US4710508A (en) * 1986-12-08 1987-12-01 Warner-Lambert Company O-substituted tetrahydropyridine oxime cholinergic agents
TW224042B (fr) * 1992-04-04 1994-05-21 Basf Ag
ZW8594A1 (en) * 1993-08-11 1994-10-12 Bayer Ag Substituted azadioxacycbalkenes

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Title
See references of WO9840365A1 *

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WO1998040365A1 (fr) 1998-09-17
AU6727098A (en) 1998-09-29
DE19710355A1 (de) 1998-09-17
JP2001518082A (ja) 2001-10-09
US6281209B1 (en) 2001-08-28

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