DE4411243A1 - 1-thiocarbamoyl-5-hydroxy-1,2-diazine derivs. - Google Patents
1-thiocarbamoyl-5-hydroxy-1,2-diazine derivs.Info
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- DE4411243A1 DE4411243A1 DE19944411243 DE4411243A DE4411243A1 DE 4411243 A1 DE4411243 A1 DE 4411243A1 DE 19944411243 DE19944411243 DE 19944411243 DE 4411243 A DE4411243 A DE 4411243A DE 4411243 A1 DE4411243 A1 DE 4411243A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
- C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/716—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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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
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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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)
Abstract
Description
Die Anmeldung betrifft neue Thiocarbamoyl-Verbindungen, deren Herstellung und deren Verwendung zum Schutz von technischen Materialien.The application relates to new thiocarbamoyl compounds, their preparation and their use to protect technical materials.
Thiocarbamoyl-Verbindungen und deren Verwendung im Materialschutz sind bekannt und werden z. B. in (DE 41 17 385) beschrieben. Diese Verbindungen haben aber den Nachteil, daß sie eine nicht immer ausreichende mikrobizide Wirkung haben und darüber hinaus aus den zu schützenden Materialien ausgewaschen werden. Ein Langzeitschutz ist durch diese bekannten Verbindungen daher nicht gewährleistet.Thiocarbamoyl compounds and their use in material protection known and z. B. described in (DE 41 17 385). These connections but have the disadvantage that they are not always a sufficient microbicidal Have an effect and also from the materials to be protected be washed out. Long-term protection is provided by these known connections therefore not guaranteed.
Gegenstand der Anmeldung sind daher die neuen Thiocarbamoyl-Verbindungen der Formel (I)The application therefore relates to the new thiocarbamoyl compounds of formula (I)
in denen
R¹, R², R³ jeweils unabhängig voneinander für Wasserstoff oder Methyl stehen
und
R⁴ für Cyclopentyl oder Cyclopentenyl steht,
n für die Zahl 0 oder 1 steht,
sowie deren Metallsalzkomplexe und Säureadditionsprodukte.in which
R¹, R², R³ each independently represent hydrogen or methyl and
R⁴ represents cyclopentyl or cyclopentenyl,
n represents the number 0 or 1,
as well as their metal salt complexes and acid addition products.
Besonders bevorzugt sind Verbindungen der Formel (I), in denen R¹, R² und R³ für Wasserstoff stehen und n für die Zahl 0 steht und insbesondere die Verbindung der Formel (I), in der R¹, R², R³ für Wasserstoff stehen, n für die Zahl 0 steht, R⁴ für Cyclopentyl steht.Compounds of formula (I) are particularly preferred in which R¹, R² and R³ stand for hydrogen and n stands for the number 0 and in particular the compound of the formula (I) in which R¹, R², R³ are hydrogen, n is the number 0, R⁴ stands for cyclopentyl.
Die Verbindungen der Formel (I) werden erhalten, indem man Formylsäurederivate der Formel (II)The compounds of formula (I) are obtained by using formic acid derivatives of the formula (II)
in denen n, R³ und R⁴ die oben angegebenen Bedeutungen haben und R für Methyl, Ethyl, n-, i-Propyl oder n-, i-, s- oder t-Butyl steht mit Thiosemi carbaziden der Formel (III)in which n, R³ and R⁴ have the meanings given above and R for Methyl, ethyl, n-, i-propyl or n-, i-, s- or t-butyl is available with thiosemi carbazides of the formula (III)
NH₂-NH-CS-NR¹R² (III)NH₂-NH-CS-NR¹R² (III)
gegebenenfalls in Gegenwart eines Verdünnungs- bzw. Lösungsmittels und/oder einer Base umsetzt.optionally in the presence of a diluent or solvent and / or a base.
Pro Mol α-Formylessigsäurederivat setzt man dabei vorzugsweise 0,8 bis 1,0 Mol Thiosemicarbazid zu.0.8 to 1.0 mol are preferably used per mole of α-formylacetic acid derivative Thiosemicarbazide too.
Als Basen werden vorzugsweise Natriumhydroxid, Kaliumhydroxid oder Kalium tert.-butylat, vorzugsweise in etwa äquimolaren Mengen zugesetzt.Sodium hydroxide, potassium hydroxide or potassium are preferably used as bases tert-butoxide, preferably added in approximately equimolar amounts.
Als Lösungsmittel bzw. Verdünnungsmittel kommen vor allem Alkohole wie Ethanol oder aromatische Kohlenwasserstoffe wie Toluol in Frage.Above all, alcohols such as Ethanol or aromatic hydrocarbons such as toluene come into question.
Die Kondensationsreaktion wird innerhalb eines größeren Temperaturbereichs durchgeführt. Für die zuerst ablaufende Thiosemicarbazonbildung wird bei Temperaturen von 20 bis 110°C, vorzugsweise 60 bis 90°C, gearbeitet. Die nach der Basenzugabe ablaufende Cyclokondensationsreaktion wird bei Temperaturen von 20 bis 100°C, vorzugsweise 20 bis 40°C, vorgenommen.The condensation reaction occurs within a wide temperature range carried out. For the first thiosemicarbazone formation, Temperatures of 20 to 110 ° C, preferably 60 to 90 ° C, worked. The after the base addition cyclocondensation reaction takes place at temperatures from 20 to 100 ° C, preferably 20 to 40 ° C, made.
Die erfindungsgemäßen 1-Thiocarbamoyl-Verbindungen der Formel (I) werden nach bekannten Methoden aus den Reaktionsgemischen isoliert. Man geht im allgemeinen so vor, daß man die Reaktionsgemische vom Lösungsmittel befreit und den Rückstand mit wäßriger Salzsäure behandelt. Die dabei ausfallenden Pyrazole werden durch Absaugen abgetrennt. Es ist jedoch auch möglich, das Reaktionsgemisch unmittelbar in einen großen Überschuß verdünnter Salzsäure einzugießen und die als Niederschlag sich abscheidenden Pyrazole abzufiltrieren.The 1-thiocarbamoyl compounds of formula (I) according to the invention isolated from the reaction mixtures by known methods. You go in generally so that the reaction mixtures are freed from the solvent and treated the residue with aqueous hydrochloric acid. The failing Pyrazoles are removed by suction. However, it is also possible that Reaction mixture immediately diluted in a large excess of hydrochloric acid pour in and filter off the precipitating pyrazoles.
Die Thiosemicarbazide der Formel (III) sind bekannt oder nach allgemein bekannten Herstellungsverfahren erhältlich.The thiosemicarbazides of the formula (III) are known or generally known manufacturing process available.
Die Formylsäurederivate der Formel (II) sind neu und ebenfalls Gegenstand der Anmeldung.The formyl acid derivatives of the formula (II) are new and also the subject of Registration.
Sie werden erhalten, in dem man Ester der Formel (IV)They are obtained by using esters of the formula (IV)
R⁴-(CH₂)n-CH₂-COOR (IV)R⁴- (CH₂) n -CH₂-COOR (IV)
in denen R⁴, n und R die oben angegebene Bedeutung haben,
mit Basen, wie z. B. NaH, in Lösungs- bzw. Verdünnungsmitteln, wie
z. B. Cyclohexan und DMF, mit Aminsäureestern, wie Methyl- oder Ethylester
formyliert.in which R⁴, n and R have the meaning given above,
with bases such as B. NaH, in solvents or diluents, such as. As cyclohexane and DMF, formylated with amino acid esters, such as methyl or ethyl esters.
Die Formylsäurederivate der Formel (II) werden auch erhalten, indem man entsprechende α,β-ungesättigte Ester nach allgemein bekannten Methoden, wie z. B. in EP-417.597 oder DE-2.643.205 beschrieben, hydroformyliert.The formyl acid derivatives of formula (II) are also obtained by corresponding α, β-unsaturated esters according to generally known methods, such as e.g. B. described in EP-417.597 or DE-2.643.205, hydroformylated.
Die Wirkstoffe der Formel (I) und die erfindungsgemäßen Mittel weisen eine starke mikrobizide Wirkung auf und können zur Bekämpfung von unerwünschte Mikroorganismen praktisch eingesetzt werden. Die Wirkstoffe der Formel (I) und die erfindungsgemäßen Mittel sind zum Schutz von technischen Materialien gegen Befall und Zerstörung durch unerwünschte Mikroorganismen geeignet.The active compounds of the formula (I) and the agents according to the invention have a strong microbicidal effect and can help fight unwanted Microorganisms can be used practically. The active ingredients of formula (I) and the agents according to the invention are for the protection of technical materials against Infestation and destruction by unwanted microorganisms are suitable.
Unter technischen Materialien sind im vorliegenden Zusammenhang nicht-lebende Materialien zu verstehen, die für die Verwendung in der Technik zubereitet worden sind. Beispielsweise können technische Materialien, die durch erfindungs gemäße Wirkstoffe vor mikrobieller Veränderung oder Zerstörung geschützt wer den sollen, Klebstoffe, Leime, Papier und Karton, Textilien, Leder, Holz, Anstrich mittel und Kunststoffartikel, Kühlschmierstoffe und andere Materialien sein, die von Mikroorganismen befallen oder zersetzt werden können. Im Rahmen der zu schützenden Materialien seien auch Teile von Produktionsanlagen, beispielsweise Kühlwasserkreisläufe, genannt, die durch Vermehrung von Mikroorganismen beein trächtigt werden können. Im Rahmen der vorliegenden Erfindung seien als tech nische Materialien vorzugsweise Klebstoffe, Leime, Papiere und Kartone, Leder, Holz, Anstrichmittel, Kühlschmiermittel und Wärmeübertragungsflüssigkeiten ge nannt, besonders bevorzugt Anstrichmittel.In the present context, technical materials include non-living ones Understand materials prepared for use in engineering have been. For example, technical materials through fiction appropriate active substances are protected against microbial change or destruction They are supposed to be adhesives, glue, paper and cardboard, textiles, leather, wood, paint medium and plastic articles, cooling lubricants and other materials that can be attacked or decomposed by microorganisms. As part of the Protective materials are also parts of production facilities, for example Cooling water circuits, called, which affect by multiplication of microorganisms can be pregnant. In the context of the present invention as tech African materials preferably adhesives, glues, papers and boxes, leather, Wood, paints, coolants and heat transfer fluids called, particularly preferably paints.
Als Mikroorganismen, die einen Abbau oder eine Veränderung der technischen Materialien bewirken können, seien beispielsweise Bakterien, Pilze, Hefen, Algen und Schleimorganismen genannt. Vorzugsweise wirken die erfindungsgemäßen Wirkstoffe bzw. Mittel gegen Pilze, insbesondere Schimmelpilze, holzverfärbende und holzzerstörende Pilze (Basidiomyceten) sowie gegen Schleimorganismen und Algen.As microorganisms that break down or change the technical Materials can cause, for example, bacteria, fungi, yeast, algae and called mucus organisms. The ones according to the invention preferably act Active ingredients or agents against fungi, in particular mold, wood-staining and wood-destroying fungi (Basidiomycetes) as well as against slime organisms and Seaweed.
Es seien beispielsweise Mikroorganismen der folgenden Gattungen genannt:For example, microorganisms of the following genera may be mentioned:
Alternaria, wie Alternaria tenuis,
Aspergillus, wie Aspergillus niger,
Chaetomium, wie Chaetomium globosum,
Coniophora, wie Coniophora puetana,
Lentinus, wie Lentinus tigrinus,
Penicillium, wie Penicillium glaucum,
Polyporus, wie Polyporus versicolor,
Aureobasidium, wie Aureobasidium pullulans,
Sclerophoma, wie Sclerophoma pityophila,
Trichoderma, wie Trichoderma viride,
Escherichia, wie Escherichia coli,
Pseudomonas, wie Pseudomonas aeruginosa,
Staphylococcus, wie Staphylococcus aureus.Alternaria, such as Alternaria tenuis,
Aspergillus, such as Aspergillus niger,
Chaetomium, like Chaetomium globosum,
Coniophora, such as Coniophora puetana,
Lentinus, such as Lentinus tigrinus,
Penicillium, such as Penicillium glaucum,
Polyporus, such as Polyporus versicolor,
Aureobasidium, such as Aureobasidium pullulans,
Sclerophoma, such as Sclerophoma pityophila,
Trichoderma, like Trichoderma viride,
Escherichia, such as Escherichia coli,
Pseudomonas, such as Pseudomonas aeruginosa,
Staphylococcus, such as Staphylococcus aureus.
Die Wirkstoffe der Formel (I) können in Abhängigkeit von ihren jeweiligen physikalischen und/oder chemischen Eigenschaften in übliche Formulierungen übergeführt werden, wie Lösungen, Emulsionen, Suspensionen, Pulver, Schäume, Pasten, Granulate, Aerosole und Feinstverkapselungen in polymeren Stoffen.The active compounds of the formula (I) can, depending on their respective physical and / or chemical properties in common formulations are transferred, such as solutions, emulsions, suspensions, powders, foams, Pastes, granules, aerosols and very fine encapsulations in polymeric substances.
Diese Formulierungen werden in bekannter Weise hergestellt, z. B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln, unter Druck stehenden verflüssigten Gasen und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln. Im Falle der Benutzung von Wasser als Streckmittel können z. B. auch organische Lösungsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen in Frage: Aromaten, wie Xylol, Toluol, Alkylnaphthaline, chlorierte Aromaten oder chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chlorethylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclo hexan oder Paraffine, z. B. Erdölfraktionen, Alkohole, wie Butanol oder Glykol sowie deren Ether und Ester, Ketone, wie Aceton, Methylethylketon, Methyl isobutylketon oder Cyclohexanon, stark polare Lösungsmittel, wie Dimethyl formamid oder Dimethylsulfoxid, sowie Wasser; mit verflüssigten gasförmigen Streckmitteln oder Trägerstoffen sind solche Flüssigkeiten gemeint, welche bei normaler Temperatur und unter Normaldruck gasförmig sind, z. B. Aerosol-Treib gase, wie Halogenkohlenwasserstoffe sowie Butan, Propan, Stickstoff und Kohlen dioxid; als feste Trägerstoffe kommen in Frage: z. B. natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quartz, Attapulgit. Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Alu miniumoxid und Silikate; als feste Trägerstoffe für Granulate kommen in Frage: z. B. gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und orga nischen Mehlen sowie Granulate aus organischem Material wie Sägemehl, Kokos nußschalen, Maiskolben und Tabakstengel; als Emulgier- und/oder schaumerzeu gende Mittel kommen in Frage: z. B. nicht ionogene und anionische Emulgatoren, wie Polyoxyethylen-Fettsäureester, Polyoxyethylen-Fettalkohol-Ether, z. B. Alkyl arylpolyglykolether, Alkylsulfonate Alkylsulfate Arylsulfonate sowie Eiweiß hydrolysate; als Dispergiermittel kommen in Frage: z. B. Ligninsulfitablaugen und Methylcellulose.These formulations are prepared in a known manner, e.g. B. by Mixing the active ingredients with extenders, i.e. liquid solvents, under Pressurized liquefied gases and / or solid carriers, if necessary using surface-active agents, ie emulsifiers and / or Dispersing agents and / or foaming agents. In case of use of water as an extender can e.g. B. also organic solvents Auxiliary solvents can be used. As liquid solvents come in essential in question: aromatics, such as xylene, toluene, alkylnaphthalenes, chlorinated Aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chlorethylene or methylene chloride, aliphatic hydrocarbons, such as cyclo hexane or paraffins, e.g. B. 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 dimethyl formamide or dimethyl sulfoxide, as well as water; with liquefied gaseous Extenders or carriers are those liquids which mean normal temperature and under normal pressure are gaseous, e.g. B. aerosol propellant gases such as halogenated hydrocarbons as well as butane, propane, nitrogen and coal dioxide; as solid carriers come into question: B. natural stone powder, such as Kaolins, clays, talc, chalk, quartz, attapulgite. Montmorillonite or Diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum minium oxide and silicates; as solid carriers for granules are: e.g. B. broken and fractionated natural rocks such as calcite, marble, pumice, Sepiolite, dolomite and synthetic granules from inorganic and orga nical flours and granules made of organic material such as sawdust, coconut nutshells, corn cobs and tobacco stalks; as emulsifying and / or foaming agents The following funds are possible: B. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkyl aryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates; as dispersants come into question: z. B. lignin sulfite and Methyl cellulose.
Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natürliche und synthetische, pulverige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospholipide, wie Kephaline und Lecithine und synthetische Phos pholipide. Weitere Additive können mineralische und vegetabile Öle sein.In the formulations, adhesives such as carboxymethyl cellulose, natural and synthetic, powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phos pholipid. Other additives can be mineral and vegetable oils.
Es können Farbstoffe wie anorganische Pigmente, z. B. Eisenoxid, Titanoxid, Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo- und Metallphthalo cyaninfarbstoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden.Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo and metal phthalalo cyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, Cobalt, molybdenum and zinc can be used.
Bevorzugt werden die erfindungsgemäßen Wirkstoffe der Formel (I) zum Schutz von Anstrichen gegen Befall und Zerstörung durch unerwünschte Mikroorga nismen eingesetzt.The active compounds of the formula (I) according to the invention are preferred for protection of coatings against infestation and destruction by unwanted microorganisms nisms used.
Unter Anstrich ist im vorliegenden Zusammenhang eine aus Anstrichstoffen hergestellte Beschichtung auf einem Untergrund zu verstehen. Der Anstrich kann mehr oder weniger in den Untergrund eingedrungen sein. Er kann aus einer oder mehreren Schichten bestehen und durch Verfahren wie Streichen, Spritzen, Tauchen, Fluten oder ähnliche Verfahren hergestellt werden.In the present context, paint is one made of paint to understand the coating produced on a substrate. The painting can more or less penetrated into the underground. It can consist of one or consist of several layers and by processes such as painting, spraying, Dipping, flooding or similar processes can be produced.
Die Verbindungen der Formeln (I) werden in die Anstrichmittel oder in Vorpro dukte zur Herstellung der Anstrichmittel nach üblichen Methoden, z. B. durch Ver mischen der Wirkstoffe mit den anderen Komponenten, eingearbeitet.The compounds of the formulas (I) are in the paint or in prepro products for the production of paints by conventional methods, e.g. B. by Ver mix the active ingredients with the other components, incorporated.
Erfindungsgemäße Anstrichmittel enthalten daher neben mindestens einem fungizi den Wirkstoff der Formel (I) allgemein übliche Anstrichkomponenten in z. B. flüssiger, pastöser oder pulverförmiger Form wie z. B.Paints according to the invention therefore contain at least one fungizi the active ingredient of formula (I) common paint components in z. B. liquid, pasty or powdery form such as B.
- - Farbmittel, wie Pigmente oder Farbstoffe, bevorzugt Pigmente. Beispielsweise genannt sei Titandioxid, Zinkoxid und Eisenoxid.- Colorants, such as pigments or dyes, preferably pigments. Examples include titanium dioxide, zinc oxide and iron oxide.
- - Bindemittel, wie beispielsweise oxidativ trocknende Alkydharze Vinyl polymerisate und Vinylcopolymerisate, Acrylpolymerisate und Acrylco polymerisate, Kunststoffpulver, Novolacke, Aminoharze, Polyesterharze, Epoxidharze, Silikonharze, Isocyanatharze bevorzugt sind Vinylpolymeri sate und Vinylcopolymerisate, Acrylpolymerisate und Acrylcopolymerisate und andere in Wasser verdünnbaren Anstrichstoffen verwendbare Binde mittel.- Binders, such as, for example, oxidative drying alkyd resins vinyl polymers and vinyl copolymers, acrylic polymers and Acrylco polymers, plastic powders, novolaks, amino resins, polyester resins, Epoxy resins, silicone resins, isocyanate resins are preferred vinyl polymers sate and vinyl copolymers, acrylic polymers and acrylic copolymers and other bandages usable in water-thinnable paints medium.
Daneben enthalten die Anstriche gegebenenfalls folgende ZusatzstoffeThe paints may also contain the following additives
- - Füllstoffe, wie beispielsweise Schwerspat, Calcit, Dolomit und Talk,Fillers such as heavy spar, calcite, dolomite and talc,
- - Lösemittel, wie beispielsweise Alkohole, Ketone, Ester, Glykolether und aliphatische sowie aromatische Kohlenwasserstoffe,- Solvents, such as alcohols, ketones, esters, glycol ethers and aliphatic and aromatic hydrocarbons,
- - sowie Verdickungs- und Thixotropiermittel, Dispergier- und Netzmittel, Trockenstoffe, Hautverhütungsmittel, Verlaufmittel, Antischaummittel, Korrosionsinhibitoren, UV-Absorber, Duftstoffe, Antistatika, Frostschutz mittel.- as well as thickening and thixotropic agents, dispersing and wetting agents, Drying agents, skin contraceptives, leveling agents, anti-foaming agents, Corrosion inhibitors, UV absorbers, fragrances, antistatic agents, frost protection medium.
Als Anstrichmittel bzw. Vorprodukte zur Herstellung von Anstrichmitteln seien vorzugsweise folgende genannt:As paints or precursors for the production of paints preferably called the following:
- - Leime und Klebstoffe auf Basis der bekannten tierischen, pflanzlichen oder synthetischen Rohstoffe.- Glues and adhesives based on the well-known animal, vegetable or synthetic raw materials.
- - Kunststoffdispersionen wie Latexdispersionen oder Dispersionen auf Basis anderer Polymere.- Plastic dispersions such as latex dispersions or dispersions based on other polymers.
- - Stärkelösungen, -dispersionen oder -slurries oder andere auf Basis von Stärke hergestellte Produkte wie z. B. Druckverdicker.- Starch solutions, dispersions or slurries or others based on Starch products such as B. pressure thickener.
- - Slurries anderer Rohstoffe wie Farbpigmente (z. B. Eisenoxidpigmente, Rußpigmente, Titandioxidpigmente) oder Slurries von Füllstoffen wie Kaolin oder Calciumcarbonat. - Slurries of other raw materials such as color pigments (e.g. iron oxide pigments, Carbon black pigments, titanium dioxide pigments) or slurries of fillers such as Kaolin or calcium carbonate.
- - Betonadditive beispielsweise auf Basis von Melasse oder Ligninsulfonaten.- Concrete additives based, for example, on molasses or lignin sulfonates.
- - Bitumenemulsionen.- bitumen emulsions.
- - Vor- und Zwischenprodukte der chemischen Industrie, z. B. bei der Farbstoffproduktion und -lagerung.- preliminary and intermediate products of the chemical industry, e.g. B. at the Dye production and storage.
- - Tinten oder Tuschen.- inks or inks.
- - Dispersionsfarben für die Anstrichindustrie.- emulsion paints for the painting industry.
- - Schichten und Appreturen.- coats and finishes.
Die Wirksamkeit und das Wirkungsspektrum der Wirkstoffe der Formeln (I) bzw. die daraus herstellbaren Mittel, Vorprodukte oder ganz allgemein Formulierungen kann erhöht werden, wenn gegebenenfalls weitere antimikrobiell wirksame Verbindungen, Fungizide, Bakterizide, Herbizide, Insektizide oder andere Wirkstoffe zur Vergrößerung des Wirkungsspektrums oder Erzielung besonderer Effekte wie z. B. des zusätzlichen Schutzes vor Insekten zugesetzt werden. Diese Mischungen können ein breiteres Wirkungsspektrum besitzen als die erfindungs gemäßen Verbindungen.The effectiveness and spectrum of activity of the active compounds of the formulas (I) or the means, intermediate products or formulations that can be produced from them can be increased if necessary further antimicrobial Compounds, fungicides, bactericides, herbicides, insecticides or others Active substances to enlarge the spectrum of effects or to achieve special ones Effects such as B. additional protection against insects. These Mixtures can have a broader spectrum of activity than the invention appropriate connections.
In vielen Fällen erhält man dabei synergistische Effekte, d. h. die Wirksamkeit der Mischung ist größer als die Wirksamkeit der Einzelkomponenten. Besonders günstige Mischungspartner sind z. B. die folgenden Verbindungen:In many cases, synergistic effects are obtained, i. H. the effectiveness of Mixing is greater than the effectiveness of the individual components. Especially favorable mix partners are e.g. B. the following connections:
Triazole wie:
Amitrole, Azocyclotin, BAS 480F, Bitertanol, Difenoconazole, Fenbuconazole,
Fenchlorazole, Fenethanil, Fluquinconazole, Flusilazole, Flutriafol, Imibenconazo
le, Isozofos, Myclobutanil, Metconazole, Epoxyconazole, Paclobutrazol, Pencon
azole, Propioconazole, (±)-cis-1-(4-chlorphenyl)-2-(1H-1,2,4-triazol-1-yl)-cyclohep
tanol, Tetraconazole, Triadimefon, Triadimenol, Triapenthenol, Triflumizole, Tri
ticonazole, Uniconazole sowie deren Metallsalze und Säureaddukte.
Triazoles such as:
Amitrole, Azocyclotin, BAS 480F, Bitertanol, Difenoconazole, Fenbuconazole, Fenchlorazole, Fenethanil, Fluquinconazole, Flusilazole, Flutriafol, Imibenconazo le, Isozofos, Myclobutanil, Metconazole, Epoxyconazole, Paclobutole, (Paclobutole) 4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) -cycloheptanol, tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole, triticonazole, uniconazole and their metal salts and acid adducts.
Imidazole wie:
Imazalil, Pefurazoate, Prochloraz, Triflumizole, 2-(1-tert-Butyl)-1-(2-chlorphenyl)-
3-(1,2,4-triazol-1yl)-propan-2-ol, Thiazolcarboxanilide wie 2′,6′-Dibromo-2-me
thyl-4-trifluoromethoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxanil-ide, 1-Imidazol
yl-1-(4′-chlorophenoxy)-3,3-dimethylbutan-2-on sowie deren Metallsalze und
Säureaddukte.
Methyl(E)-2-[2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl]3-methoxyacrylate-,
methyl(E)-2-[2-[6-(2-thioamidophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacr-y
late, methyl(E)-2-[2-[6-(2-fluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxy
acrylate, methyl(E)-2-[2-[6-(2,6-difluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-meth
oxyacrylate, methyl(E)-2-[2-[3-(pyrimidin-2-yloxy)phenoxy]phenyl]-3-meth
oxyacrylate, methyl(E)-2-[2-[3 -(5-methylpyrimidin-2-yloxy)-phenoxy]phenyl]-3-
methoxyacrylate, methyl(E)-2-[2-[3-(phenyl-sulfonyloxy)phenoxy]phenyl]-3-meth
oxyacrylate, methyl(E)-2-[2-[3-(4-nitrophenoxy)phenoxy]phenyl]-3-methoxyacry
late, methyl(E)-2-[2-phenoxyphenyl]-3-methoxyacrylate, methyl(E)-2-[2-(3,5-di
methylbenzoyl)pyrrol-1-yl]-3-methoxyacrylate, methyl(E)-2-[2-(3-methoxyphen
oxy)phenyl]-3-methoxyacrylate, methyl(E)-2-[2-(2-phenylethen-1-yl)-phenyl]-3-
methoxyacrylate, methyl(E)-2-[2-(3,5-dichlorophenoxy)pyridin-3-yl]-3-methoxy
acrylate, methyl(E)-2-(2-(3-(1,1,2,2-tetrafluoroethoxy)phenoxy)phenyl)-3-methoxy
acrylate, methyl(E)-2-(2-[3-(alpha-hydroxybenzyl)phenoxy]phenyl)-3-methoxy
acrylate, methyl(E)-2-(2-(4-phenoxypyridin-2-yloxy)phenyl)-3-methoxyacrylate,
methyl(E)-2-[2-(3-n-propyloxyphenoxy)phenyl]3-methoxyacrylate, methyl(E)-2-[2-
(3-isopropyloxyphenoxy)phenyl]-3-methoxyacrylate, methyl(E)-2-[2-[3-(2-fluoro
phenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl(E)-2-[2-(3-ethoxyphenoxy)
phenyl]-3-methoxyacrylate, methyl(E)-2-[2-(4-tert.-butylpyridin-2-yloxy)phenyl]-3-
methoxyacrylate, methyl(E)-2-[2-[3-(3-cyanophenoxy)phenoxy]phenyl] -3-methoxy
acrylate, methyl(E)-2-[2-(3-methylpyridin-2-yloxymethyl)phenyl]-3 -methoxy
acrylate, methyl(E)-2-[2-[6-(2-methylphenoxy)pyrimidin-4-yloxy]phenyl]-3-meth
oxyacrylate, methyl(E)-2-[2-(5-bromopyridin-2-yloxymethyl)phenyl]-3-methoxy
acrylate, methyl(E)-2-[2-(3-(3-iodopyridin-2-yloxy)phenoxy)phenyl]-3-methoxy
actylate, methyl(E)-2-[2-[6-(2-chloropyridin-3-yloxy)pyrimidin-4-yloxy]phenyl]-3-
methoxyacrylate, (E),(E)methyl-2-[2-(5,6-dimethylpyrazin-2-ylmethyloximinome
thyl)phenyl]-3-methoxyacrylate, (E)-methyl-2-{2-[6-(6-methylpyridin-2-yloxy)pyri
midin-4-yloxy]phenyl}-3-methoxyacrylate, (E),(E)methyl-2-{2-(3-methoxyphenyl)
methyloximinomethyl]phenyl}-3-methoxyacrylate, (E)methyl-2-{2-[6-(2-azidophen
oxy)-pyrimidin-4-yloxy]phenyl}3-methoxyacrylate, (E),(E)methyl-2-{2-[6-phenyl
pyrimidin-4-yl)-methyloximinomethyl]phenyl}-3-methoxyacrylate, (E),(E)methyl-2-
{-2-[(4-chlorophenyl)-methyloximinomethyl]phenyl}-3-methoxyacrylate, (E)methyl-
2-{2-[6-(2-n-propylphenoxy)-1,3,5-triazin-4-yloxy]phenyl}-3-methoxyacrylate,
(E),(E)methyl-2-{2-[(3-nitrophenyl)methyloximinomethyl]phenyl}--3-methoxyacry
late;
Succinat-Dehydrogenase Inhibitoren wie:
Fenfuram, Furcarbanil, Cyclafluramid, Furmecyclox, Seedvax, Metsulfovax, Pyro
carbolid, Oxycarboxin, Shirlan, Mebenil (Mepronil), Benodanil, Flutolanil (Mon
cut);
Naphthalin-Derivate wie Terbinafine, Naftifine, Butenafine, 3-Chloro-7-(2-aza-
2,7,7-trimethyl-oct-3-en-5-in);
Sulfenamide wie Dichlofluanid, Tolylfluanid, Folpet, Fluorfolpet; Captan,
Captofol;
Benzimidazole wie Carbendazim, Benomyl, Furathiocarb, Fuberidazole, Thiopho
natmethyl, Thiabendazole oder deren Salze;
Morpholinderivate wie Tridemorph, Fenpropimorph, Falimorph, Dimethomorph,
Dodemorph, Aldimorph, Fenpropidin und ihre arylsulfonsauren Salze, wie z. B. p-
Toluolsulfonsäure und p-Dodecylphenyl-sulfonsäure;
Dithiocarbamate, Cufraneb, Ferbam, Mancopper, Mancozeb, Maneb, Metam,
Metiram, Thiram Zeneb, Ziram;
Benzthiazole wie 2-Mercaptobenzothiazol;
Benzamide wie 2,6-Dichloro-N-(4-trifluoromethylbenzyl)-benzamide;
Borverbindungen wie Borsäure, Borsäureester, Borax;
Formaldehyd und Formaldehydabspaltende Verbindungen wie Benzylalkoholmono-
(poly)-hemiformal, Oxazolidine, Hexa-hydro-S-triazine, N-Methylolchloracetamid,
Paraformadehyd, Nitropyrin, Oxolinsäure, Tecloftalam;
Tris-N-(cyclohexyldiazeniumdioxy)-aluminium, N-(Cyclo-hexyldiazeniumdioxy)-tri
butylzinn bzw. K-Salze, Bis-N-(cyclohexyldiazeniumdioxy)-kupfer;
N-Methylisothiazolin-3-on, 5-Chlor-N-methylisothiazolin-3-on, 4,5-Dichloro-N-oc
tylisothiazolin-3-on, N-Octyl-isothiazolin-3-on, 4,5-Trimethylen-isothiazolinone,
4,5-Benzisothiazolinone, N-Methylolchloracetamid;
Aldehyde wie Zimtaldehyd, Formaldehyd, Glutardialdehyd, β-Bromzimtaldehyd,
Thiocyanate wie Thiocyanatomethylthiobenzothiazol, Methylenbisthiocyanat, usw;
quartäre Ammoniumverbindungen wie Benzyldimethyltetradecylammoniumchlorid,
Benzyldimethyldodecylammoniumchlorid, Didecyldimethaylammoniumchlorid;
Iodderivate wie Diiodmethyl-p-tolylsulfon, 3-Iod-2-propinyl-alkohol-4-Chlorphe
nyl-3-iodpropargylformal, 3-Brom-2,3-diiod-2-propenylethylcarbamat, 2,3,3-Triiod
allylalkohol, 3-Brom-2,3 -diiod-2-propenylalkohol, 3-Iod-2-propinyl-n-butylcarba
mat, 3-Iod-2-propinyl-n-hexylcarbamat, 3-Iod-2-propinyl-cyclohexylcarbamat, 3-
Iod-2-propinyl-phenylcarbamat;
Phenolderivate wie Tribromphenol, Tetrachlorphenol, 3-Methyl-4-chlorphenol,
3,5-Dimethyl-4-chlorphenol, Phenoxyethanol, Dichlorphen, o-Phenylphenol, m-Phe
nylphenol, p-Phenylphenol, 2-Benzyl-4-chlorphenol und deren Alkali- und
Erdalkalimetallsalze;
Mikrobizide mit aktivierter Halogengruppe wie Chloracetamid, Bronopol, Broni
dox, Tectamer wie 2-Brom-2-nitro-1,3-propandiol, 2-Brom-4′-hydroxy-acetophe
non, 2,2-Dibrom-3-nitril-propionamid, 1,2-Dibrom-2,4-dicyanobutan, β-Brom-β-
nitrostyrol;
Pyridine wie 1-Hydroxy-2-pyridinthion (und ihre Na-, Fe-, Mn-, Zn-Salze),
Tetrachlor-4-methylsulfonylpyridin, Pyrimethanol, Mepanipyrim, Dipyrithion, 1-
Hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2(1H)-pyridin;
Metallseifen wie Zinn-, Kupfer-, Zinknaphtenat, -octoat, 2-ethylhexanoat, -oleat,
-phosphat, -benzoat;
Metallsalze wie Kupferhydroxycarbonat, Natriumdichromat, Kaliumdichromat,
Kaliumchromat, Kupfersulfat, Kupferchlorid, Kupferborat, Zinkfluorosilikat,
Kupferfluorosilikat;
Oxide wie Tributylzinnoxid, Cu₂O, CuO, ZnO;
Dialkyldithiocarbamate wie Na- und Zn-Salze von Dialkyldithiocarbamaten,
Tetramethylthiuramdisulfid, Kalium-N-methyl-dithiocarbamat;
Nitrile wie 2,4,5,6-Tetrachlorisophthalodinitril, Dinatrium-cyano-dithioimidocarba
mat;
Chinoline wie 8-Hydroxychinolin und deren Cu-Salze;
Mucochlorsäure, 5-Hydroxy-2(5H)-furanon;
4,5-Dichlorodithiazolinon, 4,5-Benzdithiazolinon, 4,5-Trimethylendithiazolinon,
4,5-Dichlor-(3H)-1,2-dithiol-3-on, 3,5-Dimethyl-tetrahydro-1,3,5-thiadiazin-2-thion,
N-(2-p-Chlorbenzoylethyl)hexaminiumchlorid, Kalium-N-hydroxymethyl-N′-me
thyl-dithiocarbamat,
2-Oxo-2-(4-hydroxy-phenyl)acethydroximsäure-chlorid,
Phenyl-(2-chlor-cyan-vinyl)sulfon,
Phenyl-(1,2-dichlor-2-cyan-vinyl)sulfon;
Ag, Zn oder Cu-haltige Zeolithe allein oder eingeschlossen in polymere
Wirkstoffe.Imidazoles such as:
Imazalil, pefurazoate, prochloraz, triflumizole, 2- (1-tert-butyl) -1- (2-chlorophenyl) -3- (1,2,4-triazol-1yl) -propan-2-ol, thiazolecarboxanilides such as 2 ′ , 6'-Dibromo-2-methyl-4-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanil-ide, 1-imidazole yl-1- (4'-chlorophenoxy) -3,3- dimethylbutan-2-one and their metal salts and acid adducts.
Methyl ( E ) -2- [2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl] 3-methoxyacrylate-, methyl ( E ) -2- [2- [6- (2-thioamidophenoxy) pyrimidine -4-yloxy] phenyl] -3-methoxyacr-y late, methyl ( E ) -2- [2- [6- (2-fluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxy acrylates, methyl ( E ) -2- [2- [6- (2,6-difluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-meth oxyacrylates, methyl ( E ) -2- [2- [3- (pyrimidin-2-yloxy ) phenoxy] phenyl] -3-meth oxyacrylate, methyl ( E ) -2- [2- [3 - (5-methylpyrimidin-2-yloxy) phenoxy] phenyl] -3- methoxyacrylate, methyl ( E ) -2- [2- [3- (phenylsulfonyloxy) phenoxy] phenyl] -3-meth oxyacrylates, methyl ( E ) -2- [2- [3- (4-nitrophenoxy) phenoxy] phenyl] -3-methoxyacrylic late, methyl ( E ) -2- [2-phenoxyphenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- (3,5-di methylbenzoyl) pyrrol-1-yl] -3-methoxyacrylate, methyl ( E ) - 2- [2- (3-methoxyphen oxy) phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- (2-phenylethen-1-yl) phenyl] -3- methoxyacrylate, methyl ( E ) - 2- [2- (3,5-dichlorophenoxy) pyridin-3-yl] -3-methoxy acrylates, methyl ( E ) -2- (2- (3- (1,1,2,2-th trafluoroethoxy) phenoxy) phenyl) -3-methoxy acrylate, methyl ( E ) -2- (2- [3- (alpha-hydroxybenzyl) phenoxy] phenyl) -3-methoxy acrylate, methyl ( E ) -2- (2- (4-phenoxypyridin-2-yloxy) phenyl) -3-methoxyacrylate, methyl ( E ) -2- [2- (3-n-propyloxyphenoxy) phenyl] 3-methoxyacrylate, methyl ( E ) -2- [2- ( 3-isopropyloxyphenoxy) phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- [3- (2-fluorophenoxy) phenoxy] phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- ( 3-ethoxyphenoxy) phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- (4-tert-butylpyridin-2-yloxy) phenyl] -3- methoxyacrylate, methyl ( E ) -2- [2- [3- (3-cyanophenoxy) phenoxy] phenyl] -3-methoxy acrylates, methyl ( E ) -2- [2- (3-methylpyridin-2-yloxymethyl) phenyl] -3-methoxy acrylates, methyl ( E ) - 2- [2- [6- (2-methylphenoxy) pyrimidin-4-yloxy] phenyl] -3-meth oxyacrylates, methyl ( E ) -2- [2- (5-bromopyridin-2-yloxymethyl) phenyl] -3 -methoxy acrylates, methyl ( E ) -2- [2- (3- (3-iodopyridin-2-yloxy) phenoxy) phenyl] -3-methoxy actylate, methyl ( E ) -2- [2- [6- ( 2-chloropyridin-3-yloxy) pyrimidin-4-yloxy] phenyl] - 3-methoxyacrylates, ( E ), ( E ) methyl-2- [2- (5,6-dimethylpyrazin-2-ylmethyloximinomethyl) phenyl] -3-methoxyacrylates, ( E ) -methyl-2- {2- [6 - (6-methylpyridin-2-yloxy) pyrimidine-4-yloxy] phenyl} -3-methoxyacrylate, ( E ), ( E ) methyl-2- {2- (3-methoxyphenyl) methyloximinomethyl] phenyl} -3- methoxyacrylates, ( E ) methyl-2- {2- [6- (2-azidophen oxy) pyrimidin-4-yloxy] phenyl} 3-methoxyacrylates, ( E ), ( E ) methyl-2- {2- [6 -phenyl pyrimidin-4-yl) -methyloximinomethyl] phenyl} -3-methoxyacrylate, ( E ), ( E ) methyl-2- {-2 - [(4-chlorophenyl) -methyloximinomethyl] phenyl} -3-methoxyacrylate, ( E ) methyl- 2- {2- [6- (2-n-propylphenoxy) -1,3,5-triazin-4-yloxy] phenyl} -3-methoxyacrylate, ( E ), ( E ) methyl-2- {2 - [(3-nitrophenyl) methyloximinomethyl] phenyl} - 3-methoxyacrylic late;
Succinate dehydrogenase inhibitors such as:
Fenfuram, furcarbanil, cyclafluramide, furmecyclox, seedvax, metsulfovax, pyrocarbolide, oxycarboxin, shirlan, mebenil (mepronil), benodanil, flutolanil (mon cut);
Naphthalene derivatives such as terbinafine, naftifine, butenafine, 3-chloro-7- (2-aza-2,7,7-trimethyl-oct-3-en-5-in);
Sulfenamides such as dichlofluanid, tolylfluanid, folpet, fluorfolpet; Captan, Captofol;
Benzimidazoles such as Carbendazim, Benomyl, Furathiocarb, Fuberidazole, Thiophonatmethyl, Thiabendazole or their salts;
Morpholine derivatives such as tridemorph, fenpropimorph, falimorph, dimethomorph, dodemorph, aldimorph, fenpropidine and their arylsulfonic acid salts, such as, for. B. p-toluenesulfonic acid and p-dodecylphenyl sulfonic acid;
Dithiocarbamate, Cufraneb, Ferbam, Mancopper, Mancozeb, Maneb, Metam, Metiram, Thiram Zeneb, Ziram;
Benzothiazoles such as 2-mercaptobenzothiazole;
Benzamides such as 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide;
Boron compounds such as boric acid, boric acid ester, borax;
Formaldehyde and formaldehyde releasing compounds such as benzyl alcohol mono- (poly) hemiformal, oxazolidines, hexa-hydro-S-triazines, N-methylolchloroacetamide, paraformadehyde, nitropyrin, oxolinic acid, tecloftalam;
Tris-N- (cyclohexyldiazeniumdioxy) aluminum, N- (cyclohexyldiazeniumdioxy) tri butyltin or K salts, bis-N- (cyclohexyldiazeniumdioxy) copper;
N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, N-octyl-isothiazolin-3-one, 4,5-trimethylene -isothiazolinone, 4,5-benzisothiazolinone, N-methylolchloroacetamide;
Aldehydes such as cinnamaldehyde, formaldehyde, glutardialdehyde, β-bromocinnamaldehyde, thiocyanates such as thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate, etc;
quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, didecyldimethaylammonium chloride;
Iodine derivatives such as diiodomethyl-p-tolyl sulfone, 3-iodo-2-propynyl alcohol-4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenylethyl carbamate, 2,3,3-triiodo allyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl-n-butyl carbamate, 3-iodo-2-propynyl-n-hexyl carbamate, 3-iodo-2-propynyl cyclohexyl carbamate, 3 - iodine-2-propynylphenyl carbamate;
Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophen, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol and their Alkali and alkaline earth metal salts;
Microbicides with activated halogen group such as chloroacetamide, bronopol, broni dox, tectamer such as 2-bromo-2-nitro-1,3-propanediol, 2-bromo-4'-hydroxy-acetophe non, 2,2-dibromo-3-nitrile propionamide, 1,2-dibromo-2,4-dicyanobutane, β-bromo-β-nitrostyrene;
Pyridines such as 1-hydroxy-2-pyridinthione (and their Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine, pyrimethanol, mepanipyrim, dipyrithione, 1-hydroxy-4-methyl-6- (2nd , 4,4-trimethylpentyl) -2 (1H) pyridine;
Metal soaps such as tin, copper, zinc naphtenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate;
Metal salts such as copper hydroxycarbonate, sodium dichromate, potassium dichromate, potassium chromate, copper sulfate, copper chloride, copper borate, zinc fluorosilicate, copper fluorosilicate;
Oxides such as tributyltin oxide, Cu₂O, CuO, ZnO;
Dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates, tetramethylthiuram disulfide, potassium N-methyldithiocarbamate;
Nitriles such as 2,4,5,6-tetrachloroisophthalonitrile, disodium cyano-dithioimidocarbamate;
Quinolines such as 8-hydroxyquinoline and their Cu salts;
Mucochloric acid, 5-hydroxy-2 (5H) furanone;
4,5-dichlorodithiazolinone, 4,5-benzdithiazolinone, 4,5-trimethylene dithiazolinone, 4,5-dichloro- (3H) -1,2-dithiol-3-one, 3,5-dimethyl-tetrahydro-1,3, 5-thiadiazin-2-thione, N- (2-p-chlorobenzoylethyl) hexaminium chloride, potassium N-hydroxymethyl-N'-methyl dithiocarbamate, 2-oxo-2- (4-hydroxy-phenyl) acethydroximic acid chloride, Phenyl- (2-chloro-cyanovinyl) sulfone, phenyl- (1,2-dichloro-2-cyanovinyl) sulfone;
Zeolites containing Ag, Zn or Cu alone or included in polymeric active substances.
Ganz besonders bevorzugt sind Mischungen mit
Azaconazole, Bromuconazole, Cyproconazole, Dichlobutrazol, Diniconazole,
Hexaconazole, Metaconazole, Penconazole, Propiconazole, Tebuconazole, Methyl-
(E)-methoximino[α-(o-tolyloxy)-o-tolyl)]acetate, Methyl-(E)-2-{2-[6-(2-cyanphen
oxy)-pyrimidin-4-yl-oxy]phenyl}-3-methoxyacrylat, Methfuroxam, Carboxin, Fen
piclonil, 4-(2,2-Difluoro-1,3-benzodioxol-4-yl)-1H-pyrrol-3-carbonitril, Butenafine,
Imazalil, N-Methyl-isothiazolin-3-on, 5-Chlor-N-methylisothiazolin-3-on, N-
Octylisothiazolin-3-on, Benzisothiazolinone, N-(2-Hydroxypropyl)-amino-methanol,
Benzylalkohol-(hemi)-formal, Glutaraldehyd, Omadine, Dimethyldicarbonat,
und/oder 3-Iodo-2-propinyl-n-butylcarbamate.Mixtures with are very particularly preferred
Azaconazole, bromuconazole, cyproconazole, dichlobutrazole, diniconazole, hexaconazole, metaconazole, penconazole, propiconazole, tebuconazole, methyl- (E) -methoximino [α- (o-tolyloxy) -o-tolyl)] acetate, methyl- (E) -2 - {2- [6- (2-cyanophenoxy) -pyrimidin-4-yl-oxy] phenyl} -3-methoxyacrylate, methfuroxam, carboxin, fen piclonil, 4- (2,2-difluoro-1,3-benzodioxole -4-yl) -1H-pyrrol-3-carbonitrile, butenafine, imazalil, N-methyl-isothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, N-octylisothiazolin-3-one, benzisothiazolinones, N- (2-hydroxypropyl) amino-methanol, benzyl alcohol (hemi) formal, glutaraldehyde, omadine, dimethyl dicarbonate, and / or 3-iodo-2-propynyl-n-butyl carbamate.
Desweiteren werden auch gut wirksame Mischungen mit den folgenden Wirkstof fen hergestellt:Furthermore, well-effective mixtures with the following active ingredient fen manufactured:
Fungizide:
Acypetacs, 2-Aminobutane, Ampropylfos, Anilazine, Benalaxyl, Bupirimate,
Chinomethionat, Chloroneb, Chlozolinate, Cymoxanil, Dazomet, Diclomezine,
Dichloram, Diethofencarb, Dimethirimol, Diocab, Dithianon, Dodine, Drazoxolon,
Edifenphos, Ethirimol, Etridiazole, Fenarimol, Fenitropan, Fentin acetate, Fentin
Hydroxide, Ferimzone, Fluazinam, Fluromide, Flusulfamide, Flutriafol, Fosetyl,
Fthalide, Furalaxyl, Guazatine, Hymexazol, Iprobenfos, Iprodione, Isoprothiolane,
Metalaxyl, Methasulfocarb, Nitrothal-isopropyl, Nuarimol, Ofurace, Oxadiyl, Per
lurazoate, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Procymidone, Prop
amocarb, Propineb, Pyrazophos, Pyrifenox, Pyroquilon, Quintozene, Tar Oils, Tec
nazene, Thicyofen, Thiophanate-methyl, Tolclofos-methyl, Triazoxide, Tri
chlamide, Tricyclazole, Triforine, Vinclozolin.
Fungicides:
Acypetacs, 2-aminobutane, Ampropylfos, anilazine, benalaxyl, Bupirimate, chinomethionat, chloroneb, chlozolinate, cymoxanil, dazomet, Diclomezine, Dichloram, diethofencarb, dimethirimol, Diocab, dithianon, dodine, Drazoxolon, edifenphos, ethirimol, etridiazole, fenarimol, Fenitropan, fentin acetate, fentin hydroxide, Ferimzone, fluazinam, Fluromide, flusulfamide, flutriafol, fosetyl, Fthalide, furalaxyl, guazatine, hymexazol, iprobenfos, iprodione, isoprothiolane, metalaxyl, methasulfocarb, nitro Thal-isopropyl, nuarimol, ofurace, Oxadiyl, by lurazoate, pencycuron , Phosdiphene, Pimaricin, Piperalin, Procymidone, Prop amocarb, Propineb, Pyrazophos, Pyrifenox, Pyroquilon, Quintozene, Tar Oils, Tec nazene, Thicyofen, Thiophanate-methyl, Tolclofos-methyl, Triazoxide, Tri chlamide, Tricyclazole, Trifloroclazole, Trifluoroline
Insektizide:
Phosphorsäureester wie Azinphos-ethyl, Azinphos-methyl, α-1(4-Chlorphenyl)-4-
(O-ethyl, S-propyl)phosphoryloxy-pyrazol, Chlorpyrifos, Coumaphos, Demeton,
Demeton-S-methyl, Diazinon, Dichlorvos, Dimethoate, Ethoate, Ethoprophos,
Etrimfos, Fenitrothion, Fenthion, Heptenophas, Parathion, Parathion-methyl,
Phosalone, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothiofos,
Sulfprofos, Triazophos und Trichlorphon;
Carbamate wie Aldicarb, Bendiocarb, α-2-(1-Methylpropyl)-phenylmethylcarbamat,
Butocarboxim, Butoxycarboxim, Carbaryl, Carbofuran, Carbosulfan, Cloethocarb,
Isoprocarb, Methomyl, Oxamyl, Pirimicarb, Promecarb, Propoxur und Thiodicarb;
Organosiliciumverbindungen, vorzugsweise Dimethyl(phenyl)silyl-methyl-3-phen
oxybenzylether wie Dimethyl-(4-ethoxyphenyl)-silylmethyl-3-phenoxybenzylether
oder
(Dimethylphenyl)-silyl-methyl-2-phenoxy-6-pyridylmethylether wie z. B. Dimethyl-
(9-ethoxy-phenyl)-silylmethyl-2-phenoxy-6-pyridylmethylether oder [(Phenyl)-3-(3-
phenoxyphenyl)-propyl](dimethyl)-silane wie z. B. (4-Ethoxyphenyl)-[3-(4-fluoro-3-
phenoxyphenyl-propyl]dimethyl-silan, Silafluofen;
Pyrethroide wie Allethrin, Alphamethrin, Bioresmethrin, Byfenthrin, Cycloprothrin,
Cyfluthrin, Decamethrin, Cyhalothrin, Cypermethrin, Deltamethrin, Alpha-cyano-3-
phenyl-2-methylbenzyl-2,2-dimethyl-3-(2-chlor-2-trifluor-methylvinyl-)cyclopropan
carboxylat, Fenpropathrin, Fenfluthrin, Fenvalerate, Flucythrinate, Flumethrin,
Fluvalinate, Permethrin, Resmethrin und Tralomethrin;
Nitroimine und Nitromethylene wie 1-[(6-Chlor-3-pyridinyl)-methyl]-4,5-dihydro-
N-nitro-1H-imidazol-2-amin (Imidacloprid), N-[(6-Chlor-3-pyridyl)methyl-]N²-
cyano-N¹-methylacetamide (NI-25);
Abamectin, AC 303, 630, Acephate, Acrinathrin, Alanycarb, Aldoxycarb, Aldrin,
Amitraz, Azamethiphos, Bacillus thuringiensis, Phosmet, Phosphamidon,
Phosphine, Prallethrin, Propaphos, Propetamphos, Prothoate, Pyraclotos Pyre
thrins, Pyridaben, Pyridafenthion, Pyriproxyfen, Quinalphos, RH 7988, Rotenone,
Sodium fluoride, Sodium hexafluorosilicate, Sulfotep, Sulfuryl fluoride, Tar Oils,
Teflubenzuron, Tefluthrin, Temephos, Terbufos, Tetrachlorvinphos, Tetramethrin,
O-2-tert.-Butyl-pyrimidin-5-yl-o-isopropyl-phosphorothiate, Thiocyclam, Thio
fanox, Thiometon, Tralomethrin, Triflumuron, Trimethacarb, Vamidothion, Verti
cillium Lacanii, XMC, Xylylcarb, Benfuracarb, Bensultap, Bifenthrin, Bioallethrin,
MERbioallethrin (S)-cyclopentenyl isomer, Bromophos, Bromophos-ethyl, Bupro
fezin, Cadusafos, Calcium Polysulfide, Carbophenothion, Cartap, Chinomethionat,
Chlordane, Chlorfenvinphos Chlorfluazuron, Chlormephos, Chloropicrin, Chlor
pyrifos Cyanophos. Beta-Cyfluthrin, Alpha-cypermethrin Cyophenothrin, Cyrom
azine, Dazomet, DDT, Demeton-S-methylsulphon, Diafenthiuron, Dialifos, Di
crotophos, Diflubenzuron, Dinoseb, Deoxabenzofos, Diaxacarb, Disulfoton,
DNOC, Empenthrin, Endosulfan, EPN, Esfenvalerate, Ethiofencarb, Ethion,
Etofenprox, Fenobucarb, Fenoxycarb, Fensulfothion, Fipronil, Flucycloxuron,
Flufenprox, Flufenoxuron, Fonofos, Formetanate, Formothion, Fosmethilan, Fura
thiocarb, Heptachlor, Hexaflumuron, Hydramethylnon, Hydrogen Cyanide, Hydro
prene, IPSP, Isazofos, Isofenphos, Isoprothiolane, Isoxathion, Iodfenphos,
Kadethrin, Lindane, Malathion, Mecarbam, Mephosfolan. Mercurous, chloride,
Metam, Metarthizium, anisopliae, Methacrifos, Methamidophos, Methidathion,
Methiocarb, Methoprene, Methoxychlor, Methyl isothiocyanate, Metholcarb,
Mevinphos, Monocrotophos, Naled, Neodiprion sertifer NPV, Nicotine,
Omethoate, Oxydemeton-methyl, Pentachlorophenol, Petroleum oils, Phenothrin,
Phenthoate, Phorate;
Molluscicide:
Fentinacetate, Metaldehyde, Methiocarb, Niclosamide, Thiodicarb, Trimethacarb.Insecticides:
Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, α-1 (4-chlorophenyl) -4- (O-ethyl, S-propyl) phosphoryloxy-pyrazole, chlorpyrifos, Coumaphos, Demeton, Demeton-S-methyl, diazinon, dichlorvos, Dimethoate, Ethoate, Ethoprophos, Etrimfos, Fenitrothion, Fenthion, Heptenophas, Parathion, Parathion-methyl, Phosalone, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothiofos, Sulfprofos, Triazophos and Trichlorphon;
Carbamates such as aldicarb, bendiocarb, α-2- (1-methylpropyl) phenylmethyl carbamate, butocarboxime, butoxycarboxime, carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarb;
Organosilicon compounds, preferably dimethyl (phenyl) silylmethyl-3-phenoxybenzyl ether such as dimethyl- (4-ethoxyphenyl) -silylmethyl-3-phenoxybenzylether or (dimethylphenyl) -silylmethyl-2-phenoxy-6-pyridylmethylether such as e.g. B. Dimethyl- (9-ethoxy-phenyl) -silylmethyl-2-phenoxy-6-pyridylmethyl ether or [(phenyl) -3- (3-phenoxyphenyl) propyl] (dimethyl) -silanes such as, for. B. (4-ethoxyphenyl) - [3- (4-fluoro-3-phenoxyphenylpropyl] dimethyl silane, silafluofen;
Pyrethroids such as Allethrin, Alphamethrin, Bioresmethrin, Byfenthrin, Cycloprothrin, Cyfluthrin, Decamethrin, Cyhalothrin, Cypermethrin, Deltamethrin, Alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- (2-chloro-2-trif -methylvinyl-) cyclopropane carboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin, resmethrin and tralomethrin;
Nitroimines and nitromethylenes such as 1 - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-N-nitro-1H-imidazol-2-amine (imidacloprid), N - [(6-chloro-3 -pyridyl) methyl-] N²-cyano-N¹-methylacetamide (NI-25);
Abamectin, AC 303, 630, Acephate, Acrinathrin, Alanycarb, Aldoxycarb, Aldrin, Amitraz, Azamethiphos, Bacillus thuringiensis, Phosmet, Phosphamidon, Phosphine, Prallethrin, Propaphos, Propetamphos, Prothoate, Pyraclotos Pyre thrinsid, Pyridroxy, Pyridaben, Pyridaben, Pyridaben, Pyridaben, Pyridabeny RH 7988, Rotenone, Sodium fluoride, Sodium hexafluorosilicate, Sulfotep, Sulfuryl fluoride, Tar Oils, Teflubenzuron, Tefluthrin, Temephos, Terbufos, Tetrachlorvinphos, Tetramethrin, O-2-tert.-Butyl-pyrimidin-5-yl-o-isopropyl phosphorothiate, thiocyclam, thio fanox, thiometone, tralomethrin, triflumuron, trimethacarb, vamidothion, verti cillium lacanii, XMC, xylylcarb, benfuracarb, bensultap, bifenthrin, bioallethrin, MERbioallethrin (s) -upromoshrophenyl (S) -bromophrin (S) -bromophrin (S) -bromophrin (S) -bromophrin (S) -bromophrin (S) -cyclophenyl Cadusafos, Calcium Polysulfide, Carbophenothion, Cartap, Chinomethionate, Chlordane, Chlorfenvinphos Chlorfluazuron, Chlormephos, Chloropicrin, Chlor pyrifos Cyanophos. Beta-Cyfluthrin, Alpha-cypermethrin Cyophenothrin, Cyrom azine, Dazomet, DDT, Demeton-S-methylsulphone, Diafenthiuron, Dialifos, Di crotophos, Diflubenzuron, Dinoseb, Deoxabenzofos, Diaxacarb, Disulfotanhrin, DNOC , Ethion, Etofenprox, Fenobucarb, Fenoxycarb, Fensulfothion, Fipronil, Flucycloxuron, Flufenprox, Flufenoxuron, Fonofos, Formetanate, Formothion, Fosmethilan, Fura thiocarb, Heptachlor, Hexaflumuron, Hydramethylnon, Hydrogen CyanideSp, Hydrogen CyanideSp, Isoxathion, Iodfenphos, Kadethrin, Lindane, Malathion, Mecarbam, Mephosfolan. Mercurous, chloride, Metam, Metarthizin, anisopliae, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methoprene, Methoxychlor, Methyl isothiocyanate, Metholcarb, Mevinphos, Monocrotophos, Naled, Neodiprion sertifer NPV, Nicotine, Omethohen, Methyl, Methachene, Oxydemetonol, Oxydemetonol Phenothrin, phenthoates, phorates;
Molluscicide:
Fentin acetates, metaldehydes, methiocarb, niclosamide, thiodicarb, trimethacarb.
Algicide:
Coppersulfate, Dichlororphen, Endothal, Fentinacetate, Quinoclamine.Algicide:
Coppersulfate, dichlororphen, Endothal, Fentinacetate, Quinoclamine.
Herbicide:
acetochlor, acifluorfen, aclonifen, acrolein, alachlor, alloxydim, ametryn,
amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam atrazine,
aziptrotryne, benazolin, benfluralin, benfuresate, bensulfuron, bensulfide,
bentazone, benzofencap, benzthiazuron, bifenox, bilanafos, borax, dichlorprop,
dichlorprop-P, diclofop, diethatyl, difenoxuron, difenzoquat, diflufenican
dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethipin, dimethylarsinic
acid, dinitramine, dinoseb, dinoseb, dinoseb acetate, dinoseb, bromacil,
bromobutide, bromofenoxim, bromoxynil, butachlor. butamifos, fuenachlor,
butralin, butylate, carbetamide, CGA 184927, chlormethoxyfen, chloramben,
chlorbromuron, chlorbutam, chlorfurenol, chloridazon, chlorimuron, chlornitrofen,
chloroacetic acid, achloropicrin, chlorotoluron, chloroxuron, chlorprepham,
chlorsulfuron, chlorthal, chlorthiamid, cinmethylin cinofulsuron, clethodim,
clomazone, clomeprop, clopyralid cyanamide, cyanazine dinoseb acetate,
dinoterb, diphenamid, dipropetryn, diquat dithiopyr, diduron, DNOC, PPX-A 788,
DPX-E96361, DSMA, eglinazine, endothal, EPTC. esprocarb, ethalfluralin,
ethidimuron, ethofumesate, fenoxaprop, fenoxaprop-P, fenuron, flamprop,
flamprop-M, flazasulfuron, fluazifop, fluazifop-P, fluchloralin, flumeturon,
fluorocgycofen, fluoronitrofen, flupropanate, flurenol, fluridone, flurochloridone,
fluoroxypyr, cycloate, cycloxydim, 2,4-D, daimuron, dalapon, dazomet, 2,4-DB,
desmedipham, desmetryn, dicamba, dichlorbenil, isoproturon, isouron, isoxaben,
isoxapyrifop, lactofen, lenacil, linuron, LS830556, MCPA, MCPA-thioethyl,
MCPB, mecoprop, mecoprop-P, mefenacet, mefluidide, metam, metamitron,
metazachlor, methabenzthiazuron, methazole, methoproptryne, methyldymron,
methylisothiocyanate, metobromuron, fomosafen, fosamine, furyloxyfen,
glufosinate, glyphosate, haloxyfop, hexazinone, imazamethabenz, imazapyr,
imazaquin, imazethapyr, ioxynil, isopropalin, propyzamide, prosulfocab,
pyrazolynate, pyrazolsulfuron, pyrazoxyfen, pyributicarb, pyridate, quinclorac,
quinmerac, quinocloamine, quizalofop, quzizalofop-P, S-23 121, sethoxydim,
sifuron, simazine, simetryn, SMY 1500, sodium chlorate, sulfometuron, tar oils,
TCA, metolachlor, metoxuron, metribzin, metsulfuron, molinate, monalide,
monolinuron, MSMA, naproanilide, napropamide, naptalam, neburon, nicosulfuron,
nipyraclofen, norflurazon, orbencarb, oaryzalin, oxadiazon, oxyfluorfen, paraquat,
pebulate, pendimethalin, pentachlorophenol, pentaochlor, petroleum oils,
phenmedipham, pidoram, piperophos, pretilachlor, primisulfuron, prodiamine,
proglinazine, propmeton, prometryn, propachlor, tebutam, tebuthiuron, terbacil,
terbumeton, terbuthylazine, terbutryn, thiazafluoron, thifensulfuron, thiobencarb,
thiocarbazil, tioclorim, tralkoxydim, tri-allate, triasulfuron, tribenzuron, triclopyr,
tridiphane, trietazine, trifluralin, IBI C4874 vernolate. propanil, propaquizafop,
propazine, propham.Herbicide:
acetochlor, acifluorfen, aclonifen, acrolein, alachlor, alloxydim, ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam atrazine, aziptrotryne, benazolin, benfluralin, benfuresate, bensulfuron, bensulfide, benzafthoxane, benzafone, benzafone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzafone, benzazone, benzazone benzax dichlorprop, dichlorprop-P, diclofop, diethatyl, difenoxuron, difenzoquat, diflufenican dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethipin, dimethylarsinic acid, dinitramine, dinoseb, dinoseb, dinoseb acetate, dinoseb, bromoboxomomilil, bromomoxilomoblomomilil, bromomoxilomone, bromomoxilomone, bromomoxilomone, bromomoxilomone, bromomoxilomone, bromomoxilomone, bromomoxilomone, bromomoxilomone, bromomoxilomone, bromomoxilomate, butamifos, fuenachlor, butralin, butylate, carbetamide, CGA 184927, chlormethoxyfen, chloramben, chlorbromuron, chlorbutam, chlorfurenol, chloridazon, chlorimuron, chlornitrofen, chloroacetic acid, achloropicrin, chlorotoluron, chloroxuron, chlorprepham, chlorsulfuron, chlorthal, chlorthiamid, cinmethylin cinofulsuron, clethodim , clomazone, clomeprop, clopyralid cyanamide, cyanazine dinoseb acetate, dinoterb, diphenamid, dipropetryn, diquat dithiopyr, diduron, DNOC, PPX-A 788, DPX-E96361, DSMA, eglinazine, endothal, EPTC. esprocarb, ethalfluralin, ethidimuron, ethofumesate, fenoxaprop, fenoxaprop-P, fenuron, flamprop, flamprop-M, flazasulfuron, fluazifop, fluazifop-P, fluchloralin, flumeturon, fluorocgycofen, fluoronitrofen, flupropanate, cycloneolone, floneolurone, flurenoloxuridate, flurenolurone, flurenoloxuridate, flurenoloxuridate, flurenoloxate, flurenolurone, flurenoloxate, flurenolurone, flurenolate, flurenolurone, flurenolurone, flurenolurone, flurenolurone, flurenolurone, flurenolurone, flurenolurone, flurenolurone, flurenolate, flurenoloxyridate, flurenolurone, flurenolurone, cyclone cycloxydim, 2,4-D, daimuron, dalapon, dazomet, 2,4-DB, desmedipham, desmetryn, dicamba, dichlorbenil, isoproturon, isouron, isoxaben, isoxapyrifop, lactofen, lenacil, linuron, LS830556, MCPA, MCPA-thioethyl, MCPB, mecoprop-p, mefenacet, mefluidide, metamitron, metazachlor, methazole, methylisothiocyanate, metobromuron, fomosafen, imphamazone imazethapyr, ioxynil, isopropalin, propyzamide, prosulfocab, pyrazolynate, pyrazolsulfuron, pyrazoxyfen, pyributicarb, pyridate, quinclorac, quinmerac, quinocloamine, quizalofop, quzizalofop-P, S-23 121, sethoxy dim, sifuron, simazine, simetryn, SMY 1500, sodium chlorate, sulfometuron, tar oils, TCA, metolachlor, metoxuron, metribzin, metsulfuron, molinate, monalide, monolinuron, MSMA, naproanilide, napropamide, naptalam, neburon, noripulfuron, nyosulfuron, , orbencarb, oaryzalin, oxadiazon, oxyfluorfen, paraquat, pebulate, pendimethalin, pentachlorophenol, pentaochlor, petroleum oils, phenmedipham, pidoram, piperophos, pretilachlor, primisulfuron, prodiamine, proglinazine, propmeton, terbuthynutam, terbuthynutamon, propachloron terbuthylazine, terbutryn, thiazafluoron, thifensulfuron, thiobencarb, thiocarbazil, tioclorim, tralkoxydim, tri-allate, triasulfuron, tribenzuron, triclopyr, tridiphane, trietazine, trifluralin, IBI C4874 vernolate. propanil, propaquizafop, propazine, propham.
Die Gewichtsverhältnisse der Wirkstoffe in diesen Wirkstoffkombinationen können in relativ großen Bereichen variiert werden.The weight ratios of the active ingredients in these combinations of active ingredients can can be varied in relatively large ranges.
Vorzugsweise erhalten die Wirkstoffkombinationen den Wirkstoff der Formel (I) zu 0,1 bis 99,9%, insbesondere zu 1 bis 75%, besonders bevorzugt 5 bis 50%, wobei der Rest zu 100% durch einen oder mehrere der obengenannten Mischungspartner ausgefüllt wird.The active compound combinations preferably contain the active compound of the formula (I) 0.1 to 99.9%, in particular 1 to 75%, particularly preferably 5 to 50%, the rest being 100% by one or more of the above Mix partner is filled out.
Die zum Schutz der technischen Materialien verwendeten mikrobiziden Mittel oder Konzentrate enthalten den Wirkstoff bzw. die Wirkstoffkombination in einer Konzentration von 0,01 und 95 Gew.-%, insbesondere 0,1 bis 60 Gew.-%.The microbicidal agents used to protect the technical materials or Concentrates contain the active ingredient or combination of active ingredients in one Concentration of 0.01 and 95 wt .-%, in particular 0.1 to 60 wt .-%.
Die Anwendungskonzentrationen der zu verwendenden Wirkstoffe bzw. der Wirkstoffkombinationen richtet sich nach der Art und dem Vorkommen der zu bekämpfenden Mikroorganismen sowie nach der Zusammensetzung des zu schüt zenden Materials. Die optimale Einsatzmenge kann durch Testreihen ermittelt wer den. Im allgemeinen liegen die Anwendungskonzentrationen im Bereich von 0,001 bis 5 Gew.-%, vorzugsweise von 0,05 bis 1,0 Gew.-%, bezogen auf das zu schüt zende Material.The application concentrations of the active ingredients to be used or Active ingredient combinations depend on the type and occurrence of the combating microorganisms and according to the composition of the to protect material. The optimal amount can be determined by test series the. In general, the application concentrations are in the range of 0.001 to 5 wt .-%, preferably from 0.05 to 1.0 wt .-%, based on the pouring material.
Die erfindungsgemäßen Wirkstoffe bzw. Mittel ermöglichen in vorteilhafter Weise, die bisher verfügbaren mikrobiziden Mittel durch effektivere zu ersetzen. Sie zeigen eine gute Stabilität und haben in vorteilhafter Weise ein breites Wirkungs spektrum.The active substances or agents according to the invention advantageously enable to replace the previously available microbicidal agents with more effective ones. she show good stability and advantageously have a broad effect spectrum.
Die nachfolgenden Beispiele dienen zur Verdeutlichung der Erfindung. Die Erfin dung ist nicht auf die Beispiele beschränkt.The following examples serve to illustrate the invention. The Erfin is not limited to the examples.
8 g 2-Formyl-2-cyclopentylessigsäureethylester, hergestellt aus der käuflichen 2- Cyclopentenessigsäure durch Verestern und Formylieren auf bekannten Wegen, wurden in 70 ml Ethanol mit 3,9 g Thiosemicarbazid 4 Stunden refluziert und nach Versetzen mit 4,8 g Kalium-tert.-butylat ca. 12 Stunden stehen gelassen. Aufgießen auf Eis /10% HCl ergibt 2,5°C der Zielverbindung vom Schmelzpunkt F: 160°C.8 g of 2-formyl-2-cyclopentylacetic acid ethyl ester, prepared from the commercially available 2- Cyclopentenacetic acid by esterification and formylation in known ways, were refluxed in 70 ml of ethanol with 3.9 g of thiosemicarbazide for 4 hours and after adding 4.8 g of potassium tert-butoxide, let stand for about 12 hours. Pouring on ice / 10% HCl gives 2.5 ° C of the target compound from the melting point F: 160 ° C.
Analog Beispiel 1 erhält man die Verbindung vom Schmelzpunkt F. 152°C.Analogously to Example 1, the compound of melting point F. 152 ° C. is obtained.
40,7 g 3-Cyclopropylpropionsäureethylester werden in 400 ml DMF bei 0 bis 5°C vorgelegt und mit 14,4 g Natriumhydrid (80%ig in Öl) versetzt. Nach Zutropfen von 200 ml Ameisensäureethylester wird 24 h bei 25°C gerührt. Der Ansatz wird in 1,6 l 10% HCl eingerührt, mit 800 ml Methylenchlorid extrahiert und destilliert. Man erhält 19,7 g (41%) 2-Formyl-3-cyclopentylpropionsäureethylester vom Siedepunkt 117°C/12 mm. 40.7 g of 3-cyclopropylpropionate are in 400 ml of DMF at 0 to 5 ° C. submitted and mixed with 14.4 g of sodium hydride (80% in oil). After dropping 200 ml of ethyl formate are stirred at 25 ° C. for 24 h. The approach is going stirred in 1.6 l 10% HCl, extracted with 800 ml methylene chloride and distilled. 19.7 g (41%) of 2-formyl-3-cyclopentylpropionic acid ethyl ester are obtained from the boiling point 117 ° C / 12 mm.
9,7 g des erhaltenen Öls wurden in 80 ml Ethanol mit 4,47 g Thiosemicarbazid 4 h unter Rückfluß erhitzt, bei 25°C mit 5,5 g Kalium-tert.-butylat versetzt und 24 h gerührt. Nach Eingeben in 250 ml 10% HCl erhält man nach Umkristallisation aus Ethanol 5 g (45%) der Zielverbindung vom Schmelzpunkt 157°C.9.7 g of the oil obtained were in 80 ml of ethanol with 4.47 g of thiosemicarbazide 4 Heated under reflux, mixed with 5.5 g of potassium tert-butoxide at 25 ° C and 24 h touched. After entering 250 ml of 10% HCl, recrystallization is obtained from ethanol 5 g (45%) of the target compound with a melting point of 157 ° C.
Claims (9)
R¹, R², R³ jeweils unabhängig voneinander für Wasserstoff oder Methyl stehen und
R⁴ für Cyclopentyl oder Cyclopentenyl steht,
n für die Zahl 0 oder 1 steht,
sowie deren Metallsalzkomplexe und Säureadditionsprodukte.1. Thiocarbamoyl compounds of the formula (I) in which
R¹, R², R³ each independently represent hydrogen or methyl and
R⁴ represents cyclopentyl or cyclopentenyl,
n represents the number 0 or 1,
as well as their metal salt complexes and acid addition products.
n, R³ und R⁴ die in Anspruch 1 angegebene Bedeutung haben und
R für Methyl, Ethyl, n-, i-Propyl oder n-, s- oder t-Butyl steht.8. Formyl acid derivatives of the formula (II) in which
n, R³ and R⁴ have the meaning given in claim 1 and
R represents methyl, ethyl, n-, i-propyl or n-, s- or t-butyl.
R³, R⁴ und R die in Anspruch 8 angegebenen Bedeutungen haben, dadurch gekennzeichnet, daß man Ester der Formel (IV) R⁴-(CH₂)n-CH₂-COOR (IV)in denen R⁴, n und R die oben angegebene Bedeutung haben,
mit Basen, in Lösungs- bzw. Verdünnungsmitteln, mit Aminsäureestern formyliert.9. Process for the preparation of compounds of formula (II) in which
R³, R⁴ and R have the meanings given in Claim 8, characterized in that esters of the formula (IV) R⁴- (CH₂) n -CH₂-COOR (IV) in which R⁴, n and R have the meaning given above,
formulated with bases, in solvents or diluents, with amino acid esters.
Priority Applications (18)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19944411243 DE4411243A1 (en) | 1994-03-31 | 1994-03-31 | 1-thiocarbamoyl-5-hydroxy-1,2-diazine derivs. |
| HU9600300A HU215275B (en) | 1993-08-11 | 1994-07-29 | Microbicidal compositions containing thiocarbamoylpyrazole derivatives, novel alpha-aldehyde carboxylic acid intermediates for the preparation of the active compounds, and a method for preparing alpha-aldehyde carboxylic acids |
| BR9407232A BR9407232A (en) | 1993-08-11 | 1994-07-29 | Thiocarbamoyl compounds |
| PL94312966A PL181247B1 (en) | 1993-08-11 | 1994-07-29 | New thiocarbamoyl derivatives, a method for producing new thiocarbamoyl derivatives and an agent for the protection of industrial materials |
| AU76101/94A AU684541B2 (en) | 1993-08-11 | 1994-07-29 | Thiocarbamoyl compounds used as antimicrobial agents |
| PCT/EP1994/002534 WO1995004722A1 (en) | 1993-08-11 | 1994-07-29 | Thiocarbamoyl compounds |
| AT94926134T ATE165089T1 (en) | 1993-08-11 | 1994-07-29 | THIOCARBAMOYL COMPOUNDS AS MICROBICIDES |
| DE59405727T DE59405727D1 (en) | 1993-08-11 | 1994-07-29 | THIOCARBAMOYL COMPOUNDS AS MICROBICIDES |
| DK94926134T DK0713485T3 (en) | 1993-08-11 | 1994-07-29 | Thiocarbamoyl compounds as microbicides |
| JP7506206A JPH09501422A (en) | 1993-08-11 | 1994-07-29 | Thiocarbamoyl compounds used as antimicrobial agents |
| CN94193065A CN1082049C (en) | 1993-08-11 | 1994-07-29 | Medicaments containing thiocarbamoyl-5-hydroxy pyrazoles |
| KR1019960700644A KR100346811B1 (en) | 1993-08-11 | 1994-07-29 | Thiocarbamoyl compounds used as antimicrobial agents |
| EP94926134A EP0713485B1 (en) | 1993-08-11 | 1994-07-29 | Thiocarbamoyl compounds as microbicides |
| CZ1996396A CZ289324B6 (en) | 1993-08-11 | 1994-07-29 | Thiocarbamoyl compounds, process of their preparation, method of protecting industrial materials, microbicidal compositions in which these compositions are comprised as well as use of these compounds |
| CA002169195A CA2169195A1 (en) | 1993-08-11 | 1994-07-29 | Thiocarbamoyl compounds used as antimicrobial agents |
| NO960271A NO305556B1 (en) | 1993-08-11 | 1996-01-23 | Thiocarbamoyl compounds and their use as well as means for protecting technical materials |
| FI960588A FI960588L (en) | 1993-08-11 | 1996-02-08 | Thiocarbamoyl compounds used as microbicides |
| US08/598,878 US5672617A (en) | 1993-08-11 | 1996-02-09 | Medicaments containing 1-thiocarbamoyl-5-hydroxy-pyrazoles and their use as agents for combating septic shock |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19944411243 DE4411243A1 (en) | 1994-03-31 | 1994-03-31 | 1-thiocarbamoyl-5-hydroxy-1,2-diazine derivs. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE4411243A1 true DE4411243A1 (en) | 1995-10-05 |
Family
ID=6514350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19944411243 Withdrawn DE4411243A1 (en) | 1993-08-11 | 1994-03-31 | 1-thiocarbamoyl-5-hydroxy-1,2-diazine derivs. |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE4411243A1 (en) |
-
1994
- 1994-03-31 DE DE19944411243 patent/DE4411243A1/en not_active Withdrawn
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