Classifications

• • 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
  • C07D413/06—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 carbon chain containing only aliphatic carbon atoms
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—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
  • 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

Definitions

• the invention relates to new thiophene dioxime ethers, a process for their preparation and their use as fungicides.
• E represents optionally substituted, geminally linked thiophene diyl
• R 1 represents optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or arylalkyl,
• R 2 represents optionally substituted alkyl, alkenyl, alkynyl, aryl, cycloalkyl, arylalkyl, heterocyclyl or heterocyclylalkyl,
• R 3 represents optionally substituted alkyl or cycloalkyl, and for a single bond, oxygen, sulfur or a grouping
• R 4 represents alkyl, or together with R 2 and the nitrogen atom to which they are attached, forms an optionally substituted heterocyclic ring.
• R 1 , R 2 , R 3 and Z have the meanings given above and
• Alk stands for alkyl
• the compounds of the invention can optionally be used as mixtures of various possible isomeric forms, especially stereoisomers, such as e.g. 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.
• Carbon atoms in the aryl part and 1 to 4 carbon atoms in the alkyl part preferably being selected from the following list: halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, alkylaminoalkyl, dialkylaminoalkyl,
• Cycloalkyl or cycloalkyloxy each having 3 to 6 carbon atoms; each optionally monosubstituted to tetrasubstituted, identically or differently, by fluorine, chlorine, methyl, trifluoromethyl or ethyl and in each case doubly linked alkylene having 3 or 4 carbon atoms, oxyalkylene having 2 or 3 carbon atoms or dioxyalkylene having 1 or 2 carbon atoms; each optionally substituted by halogen, alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl having 1 to 4 carbon atoms, haloalkoxy, haloalkylthio, haloalkylsulfmyl or haloalkylsulfonyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms, phenoxy or phenylalkoxy having 1 to 4 carbon atoms in the alkyl part ,
• A represents hydrogen or alkyl having 1 to 4 carbon atoms or cycloalkyl having 3 to 6 carbon atoms and
• a ⁇ stands for hydroxy, amino, methylamino, methyl, phenyl, benzyl, alkoxy, alkylamino, dialkylamino with 1 to 4 carbon atoms in the respective alkyl chains,
• R 4 represents alkyl having 1 to 4 carbon atoms, or together with R 2 and the nitrogen atom to which they are attached, forms an optionally substituted, 3 to 6-membered, heterocyclic ring.
• saturated or unsaturated hydrocarbon chains such as alkyl
• the saturated or unsaturated hydrocarbon chains are also straight-chain or branched, also in combination with heteroatoms, such as in alkoxy or alkylthio.
• Haloalkyl stands for partially or completely halogenated alkyl. In the case of polyhalogenated haloalkyl, the halogen atoms can be the same or different.
• Preferred halogen atoms are fluorine and chlorine and especially fluorine. If the haloalkyl carries further substituents, the maximum possible number of halogen atoms is reduced to the remaining free valences.
• Halogen generally represents fluorine, chlorine, bromine or iodine, preferably
• 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 different from carbon. If the ring contains several heteroatoms, these can be the same or different. Heteroatoms are preferably oxygen, nitrogen or sulfur. If the ring contains several oxygen atoms, they are not adjacent. If appropriate, the ring-shaped compounds with further carbocyclic or heterocyclic, fused or bridged rings form together a polycycic ring system. A polycyclic ring system can be linked via the heterocyclic ring or a fused-on carbocyclic ring. Mono- or bicyclic ring systems are preferred, in particular mono- or bicyclic aromatic ring systems.
• R 1 is methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, allyl, 2-buten-l-yl, 2-methyl-2-buten-l-yl, propargyl or for cyclopentyl or cyclohexyl which is optionally up to four times substituted by fluorine, chlorine, methyl or ethyl; or for optionally substituted by methyl, ethyl, fluorine, chlorine or bromine
• Trifluoroethyl Trifluoroethyl,
• Methylamino Ethylamino, n- or i-propylamino, dimethylamino. Diethyl amino,
• Fluorine, chlorine, methyl or trifluoromethyl substituted in each case doubly linked propanediyl, ethyleneoxy, methylenedioxy, ethylenedioxy, each optionally substituted by fluorine, chlorine, methyl, trifluoromethyl or methoxy, phenoxy or benzyl, in each case optionally by halogen, alkyl, alkoxy, alkylthio,
• a ' represents hydrogen or methyl
• a 2 represents hydroxy, methoxy, ethoxy, amino, methylamino, methyl, phenyl or benzyl,
• Oxygen, sulfur or a grouping for methyl, ethyl, n- or i-propyl, or for cyclopropyl, cyclobutyl, cyclopentyl or phenyl which is optionally up to four times substituted by fluorine, chlorine, methyl or ethyl; in particular represents methyl or cyclopropyl, Z for a single bond.
• R 4 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or together with R 2 and the nitrogen atom to which they are attached, an optionally substituted 5 to 6 membered, heterocyclic ring forms.
• R 1 preferably represents ethyl and in particular methyl.
• R 3 preferably represents ethyl and in particular methyl.
• R 2 preferably represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl or phenyl which is substituted once or twice by fluorine, chlorine, methyl, methoxy, trifluoromethyl and / or trifluoromethoxy or especially for unsubstituted phenyl.
• Formula (II) provides a general definition of the esters required as starting materials for carrying out the process according to the invention for preparing the thiophene dioxime ethers of the formula (I).
• E, R 1 , R 2 , R 3 and Z have preferably or in particular those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as preferred or as particularly preferred for E, R 1 , R 2 , R 3 and Z.
• esters of the formula (II) are not yet known; they are also the subject of the present application as new substances.
• R 1 , R 2 , R 3 and Z have the meanings given above, optionally in the presence of a diluent, preferably an ether, such as tetrahydrofuran, a nitrile, such as acetonitrile, an amide, such as N, N-dimethylformamide, or N-methylpyrrolidone; or a sulfoxide such as dimethyl sulfoxide; optionally in the presence of a base, preferably an alkaline earth metal or alkali metal hydride, or alcoholates, such as, for example, sodium hydride, sodium methylate, sodium ethylate or potassium tert-butoxide.
• a diluent preferably an ether, such as tetrahydrofuran, a nitrile, such as acetonitrile, an amide, such as N, N-dimethylformamide, or N-methylpyrrolidone
• a sulfoxide such as dimethyl
• halomethylthiophenes required as starting materials for carrying out the process according to the invention for the preparation of the esters of the formula (II) are generally defined by the formula (III).
• E preferably or in particular has those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as preferred or as particularly preferred for E.
• Alk preferably represents alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl.
• X represents halogen, preferably chlorine or bromine.
• halomethylthiophenes of the formula (III) are known and can be prepared by known methods (compare, for example, WO 95-01973 or EP-A 579 071).
• Formula (IV) provides a general definition of the oximes which are further required as starting materials for carrying out the process according to the invention for preparing the esters of formula (II).
• R 1 , R 2 , R 3 and Z preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the invention
• Formula (I) was mentioned as preferred, or as particularly preferred for R 1 , R 2 , R 3 and Z.
• the oximes of the formula (IV) are known and can be prepared by known methods (compare, for example, WO 96-32373 and WO 97-06133).
• the ethane derivatives still required as starting materials for carrying out the process according to the invention for the preparation of the thiophene dioxime ethers of the formula (I) are known synthetic chemicals.
• thiophene dioxime ethers of the formula (I) 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,
• the process according to the invention for the preparation of the thiophene dioxime ethers of the formula (I) 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 alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, 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,
• DABCO diazabicyclooctane
• DBN Diazabicyclonones
• DBU Diazabicycloundecen
• reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures from 0 ° C to 150 ° C, preferably at temperatures from 0 ° C to 80 ° C.
• reaction products are worked up, worked up and isolated using generally customary processes (see also the preparation examples).
• the substances according to the invention have a strong microbicidal action and can be used to control unwanted microorganisms, such as fungi and
• Bacteria can be used in crop protection and material protection.
• Fungicides can be used to protect plants against Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
• 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;
• 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 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
• 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 permits 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 particularly successful
• the active compounds according to the invention are also suitable for increasing the crop yield.
• the active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols,
• formulations are made in a known manner, e.g. 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.
• 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.
• surface-active agents that is to say emulsifiers and / or dispersants and / or foam-generating agents.
• water e.g. organic solvents can also be used as auxiliary solvents.
• aromatics such as
• Gaseous extenders or carriers are those liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide.
• Solid carrier materials are suitable: for example natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates.
• Possible solid carriers for granules are: e.g.
• emulsifiers and / or foaming agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates.
• Possible dispersants are, for example, lignin sulfite liquor and methyl cellulose.
• 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, 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,
• 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 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 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 -Cold and warm mist formulations.
• 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.
• Iodocarb Ipconazole, Iprobefos (IBP), Iprodione, Irumamycin, Isoprothiolan,
• Mancopper Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl,
• Metconazole methasulfocarb, methfuroxam, metiram, metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,
• Oxadixyl Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,
• Paclobutrazole pefurazoate, penconazole, pencycuron, phosdiphene, pimaricin, piperalin,
• Tebuconazole Tecloftalam, Tecnazen, Tetcyclacis, Tetraconazole, Thiabendazole, Thicyofen, Thifluzamide, Thiophanate-methyl, Thiram, Tioxymid, Tolclofos-methyl,
• Dagger G OK-8705, OK-8801, ⁇ - (1, 1-dimethylethyl) -ß- (2-phenoxyethyl) - 1 H-1, 2,4-triazole-1-ethanol, ⁇ - (2,4-dichloro-phenyl) -ß-fluoro-b-propyl-1 H-1, 2,4-triazole-1-ethanol, ⁇ - (2,4-dichlo ⁇ henyl) -ß-methoxy-a-methyl-1 H-1, 2,4 -triazol-1-ethanol, ⁇ - (5-methyl-l, 3-dioxan-5-yl) -ß - [[4- (trifluoromethyl) phenyl] methylene] -lH-l, 2,4-triazole -1-ethanol,
• Ethiofencarb Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimfos, Fenamiphos, Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fenvalerate, Fipronil, Fluazinam, Fluazuron, Flubrocythrinate, Flucycloxoxinon, Flutoxinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, , Furathiocarb,
• Halofenozide HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene, Imidacloprid, Isazofos, Isofenphos, Isoxathion, Ivermectin, Kernpolyederviruses Lambda-cyhalothrin, Lufenuron
• Mecarbam Metaldehyde, Methamidophos, Metharhician anisopliae, Metharhician flavoviride, Methidathione, Methiocarb, Methomyl, Methoxyfenozide, Metolcarb, Metoxadiazone, Mevinphos, Milbemectin, Monocrotophos, Naled, Nitenpyramo, Oxitomethonid, Oxitomethonate, Oxitomethamate, Oxitomethonate, Oxitomethonate, Oxyne, Oxidonyl, Oxitone, Oxitone, Oxyne, Oxyne, Oxitone
• Paecilomyces fumosoroseus Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A, Pirimiphos M, Profenofos, Promecarb, Propoxur, Prothiofos, Prothoat, Pyymrahrofinos. Pyrethrum, pyridaben, pyridathione, pyrimidifen, pyriproxyfen,
• 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. In the case of seed treatment, 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 kilogram of seed. In the treatment of the soil, the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.
• Solvent 10 parts by weight of N, N-dimethylacetamide 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 then placed in a greenhouse at a temperature of approximately 20 ° C. and a relative atmospheric humidity of 80% in order to prevent the development of
• 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.
• Example (2) the substance according to the invention listed in Example (1) shows an efficiency of 90% or more at an application rate of 250 g / ha.
• Solvent 47 parts by weight of acetone 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%.
• Example (1) shows an efficiency of 90% or more at an application rate of 100 g / ha.

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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)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Plural Heterocyclic Compounds (AREA)
• Heterocyclic Compounds Containing Sulfur Atoms (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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Citations (2)

• 1998
  • 1998-08-01 DE DE1998134830 patent/DE19834830A1/de not_active Withdrawn
• 1999
  • 1999-07-20 JP JP2000563636A patent/JP2002522427A/ja active Pending
  • 1999-07-20 EP EP99938292A patent/EP1131309A2/de not_active Withdrawn
  • 1999-07-20 WO PCT/EP1999/005151 patent/WO2000008003A2/de not_active Application Discontinuation
  • 1999-07-20 AU AU52852/99A patent/AU5285299A/en not_active Abandoned

Patent Citations (2)

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