WO1996000723A1 - Pyridine-3-imino alkyl esters as fungicides - Google Patents

Pyridine-3-imino alkyl esters as fungicides Download PDF

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Publication number
WO1996000723A1
WO1996000723A1 PCT/EP1995/002323 EP9502323W WO9600723A1 WO 1996000723 A1 WO1996000723 A1 WO 1996000723A1 EP 9502323 W EP9502323 W EP 9502323W WO 9600723 A1 WO9600723 A1 WO 9600723A1
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Prior art keywords
formula
imino
pyridine
butyl
metal salt
Prior art date
Application number
PCT/EP1995/002323
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German (de)
French (fr)
Inventor
Herbert Gayer
Peter Gerdes
Stefan Dutzmann
Klaus Stenzel
Heinz-Wilhelm Dehne
Original Assignee
Bayer Aktiengesellschaft
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Filing date
Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to JP8502756A priority Critical patent/JPH10504805A/en
Priority to EP95924246A priority patent/EP0767784A1/en
Priority to AU28834/95A priority patent/AU2883495A/en
Publication of WO1996000723A1 publication Critical patent/WO1996000723A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C07D213/82—Amides; Imides in position 3
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings

Definitions

  • the present invention relates to new pyridine-3-imino-alkyl esters, a process for their preparation and their use as fungicides.
  • dichlorophenylimino-C- (isopropoxy) methyl-3-pyridine to combat fungi.
  • the effectiveness of this substance leaves something to be desired in some cases at low application rates.
  • R represents methyl, ethyl, n-propyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, dodecyl or methoxyethyl and
  • R 1 and R 2 independently of one another represent fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl or trifluoromethoxy,
  • R 1 and R 2 have the meanings given above,
  • the substances according to the invention are distinguished by a substantially better fungicidal action than the most similar in terms of constitution, compounds of the same indication known from the prior art.
  • the substances according to the invention exceed e.g. the 2 ', 4'-dichlorophenylimino-C- (isopropoxy) methyl-3-pyridine, which is a structurally obvious compound with the same direction of action, with regard to its fungicidal properties.
  • R preferably represents methyl, ethyl, n-propyl, n-butyl, sec-butyl, isobutyl, tert-butyl, the radicals of the formulas
  • R 1 preferably represents fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl or trifluoromethoxy.
  • R 2 preferably represents fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl or trifluoromethoxy.
  • Preferred substances according to the invention are also addition products of acids and those pyridine-3-iminoalkyl esters of the formula (I) in which R, R 1 and R 2 have the meanings given above as preferred.
  • the acids which can be added preferably include halohydric acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as acetic acid, maleic acid, Succinic acid, fumaric acid, tartaric acid, citric acid Nenoic acid, salicylic acid, sorbic acid and lactic acid as well as sulfonic acids such as p-toluenesulfonic acid, 1,5-naphthalenedisulfonic acid or camphorsulfonic acid, and also saccharin and thiosaccharin.
  • halohydric acids such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as ace
  • preferred substances according to the invention are addition products from salts of metals of the II. To IV. Main group and of I. and II. And IV. To VIII. Subgroup of the periodic table of the elements and pyridine-3-imino-alkyl esters of the formula (I ), in which R, R 1 and R 2 have the meanings given above as preferred.
  • Salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred.
  • Anions of these salts are those which are derived from acids which lead to physiologically tolerable addition products.
  • Particularly preferred such acids in this connection are the hydrohalic acids, e.g. Hydrochloric acid and hydrobromic acid, also phosphoric acid, nitric acid and sulfuric acid.
  • Examples of substances according to the invention are the pyridine-3-imino-alkyl esters listed in the following table.
  • Formula (II) provides a general definition of the imino compounds required as starting materials when carrying out the process according to the invention.
  • R 1 and R 2 preferably have those meanings which have already been mentioned preferably in connection with the description of the substances of the formula (I) according to the invention for these substituents.
  • imino compounds of the formula (II) are known or can be prepared by processes which are known in principle (cf. EP-OS 0 008 145). Thus, imino compounds of the formula (II) are obtained by using nicotinamide of the formula
  • R 1 and R 2 have the meanings given above,
  • nicotinamide of the formula (IV) are known or can be prepared by methods known in principle (cf. EP-OS 0 008 145). Nicotinic acid amides of the formula (IV) are obtained by using nicotinic acid of the formula
  • R 1 and R 2 have the meanings given above,
  • Formula (III) provides a general definition of the alcohols which are further required as starting materials when carrying out the process according to the invention.
  • R preferably has those meanings which have already been mentioned preferably for this substituent in connection with the description of the substances of the formula (I) according to the invention.
  • the alcohols of the formula (III) are generally known compounds of organic chemistry.
  • Suitable diluents for carrying out the process according to the invention are all inert organic solvents which are customary for such reactions.
  • Ethers such as diethyl ether, are preferably usable.
  • Methyl tert-butyl ether ethylene glycol dimethyl ether, tetrahydrofuran and dioxane, also nitriles, such as acetonitrile, and also optionally halogenated aliphatic, cycloaliphatic and aromatic hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, hexane, cyclohexane, benzene , Toluene, xylene and chlorobenzene.
  • nitriles such as acetonitrile
  • halogenated aliphatic, cycloaliphatic and aromatic hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, hexane, cyclohexane, benzene , Toluene, xylene and chlorobenzene.
  • Suitable acid binders for carrying out the process according to the invention are all customary inorganic or organic bases.
  • Alkali metal or alkaline earth metal hydroxides, amides, alcoholates, carbonates and hydrogen carbonates such as sodium hydroxide, potassium hydroxide, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium carbonate, potassium carbonate, calcium carbonate, potassium hydrogen carbonate and Sodium bicarbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene ( DBU).
  • DABCO diazabicyclooctane
  • DBN diazabicyclononene
  • reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures between -10 ° C and 120 ° C, preferably between 0 ° C and 100 ° C.
  • the process according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.
  • the processing takes place according to usual methods.
  • the general procedure is to concentrate the reaction mixture
  • Water and a water-immiscible organic solvent are added to the residue, the organic phase is separated off, after drying, if appropriate, concentrated, and the remaining residue is optionally further purified by recrystallization or by chromatographic means.
  • the imino compounds of the formula (II) can be used in the form of hydrohalides or as free bases when carrying out the process according to the invention.
  • the process is carried out by suspending hydrohalides, for example hydrochlorides, of imino compounds of the formula (II) in a suitable solvent, for example chloroform, by subsequent treatment with aqueous alkali metal base, for example aqueous sodium carbonate. Solution, converted into the free bases and reacting these with alcohols of the formula (HI) or their salts (alcoholates), if appropriate in the presence of a phase transfer catalyst.
  • aqueous alkali metal base for example aqueous sodium carbonate
  • the pyridine-3-iminoalkyl esters of the formula (I) according to the invention can be converted into acid addition salts or metal salt complexes.
  • Manner according to usual salt formation methods, e.g. by dissolving a compound of formula (I) in a suitable inert solvent and adding the acid, e.g. Hydrochloric acid can be obtained and in a known manner, e.g. by filtration, isolated and, if necessary, cleaned by washing with an inert organic solvent.
  • acid e.g. Hydrochloric acid
  • Metal salt complexes can be isolated in a known manner, for example by filtering off, and optionally purified by recrystallization.
  • the active compounds according to the invention have a strong microbicidal action and can be used as fungicides.
  • Fungicides are used in crop protection to combat Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.
  • Xanthomonas species such as Xanthomonas oryzae
  • Pseudomonas species such as Pseudomonas lachrymans
  • Erwinia species such as Erwinia amylovora
  • Pythium species such as Pythium ultimum
  • Phytophthora species such as Phytophthora infestans
  • Pseudoperonospora species such as Pseudoperonospora humuli or Pseudoperonospora cubensis;
  • Plasmopara species such as Plasmopara viticola
  • Peronospora species such as Peronospora pisi or P. brassicae
  • Erysiphe species such as Erysiphe graminis
  • Sphaerotheca species such as Sphaerotheca fuliginea
  • Podosphaera species such as Podosphaera leucotricha
  • Venturia species such as Venturia inaequalis
  • Pyrenophora species such as Pyrenophora teres or P. graminea; (Conidial form: Drechslera, Syn: Helminthosporium);
  • Cochliobolus species such as Cochliobolus sativus
  • Drechslera (Conidial form: Drechslera, Syn: Helminthosporium);
  • Uromyces species such as Uromyces appendiculatus
  • Puccinia species such as Puccinia recondita
  • Tilletia species such as Tilletia caries
  • Ustilago species such as Ustilago nuda or Ustilago avenae
  • Pellicularia species such as Pellicularia sasakii
  • Pyricularia species such as Pyricularia oryzae; Fusarium species, such as Fusarium culmorum; Botrytis species, such as Botrytis cinerea; Septoria species, such as Septoria nodorum; Leptosphaeria species, such as Leptosphaeria nodorum; Cercospora species, such as Cercospora canescens;
  • Alternaria species such as Alternaria brassicae
  • Pseudocercosporella species such as Pseudocercosporella herpotrichoides.
  • the active compounds according to the invention are particularly suitable for combating Pyricularia oryzae on rice and for combating cereal diseases, such as Leptosphaeria nodorum, Cochliobolus sativus, Pyrenophora teres and Erysiphe species.
  • the substances according to the invention show a very good action against Venturia, Uncinula, Sphaerotheca and Podosphaera.
  • the substances according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV formulations.
  • customary formulations such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV formulations.
  • These formulations are made in a known manner, e.g. by mixing the active ingredients with
  • Extenders that is to say liquid solvents, liquefied gases and / or solid carriers under pressure, if appropriate using 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.
  • the following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and
  • esters ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water;
  • Liquefied gaseous extenders or carriers mean liquids which are at normal temperature and are gaseous under normal pressure, for example aerosol propellants, such as butane, propane, nitrogen and carbon dioxide;
  • aerosol propellants such as butane, propane, nitrogen and carbon dioxide
  • solid carriers for example natural rock powder, such as kaolins, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates; as solid carriers for
  • Granules are possible: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foaming agents are possible: e.g. nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g.
  • Alkylaryl polyglycol ethers alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.
  • Adhesives such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also 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, molybdenum and zinc are used.
  • the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention can also be used in 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.
  • synergistic effects are obtained, i.e. the
  • the effectiveness of the mixture is greater than the effectiveness of the individual components.
  • Fenpropimorph fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil,
  • copper preparations such as: copper hydroxide, copper naphthenate,
  • Mancopper Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,
  • Probenazole prochloraz, procymidone, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilone,
  • Cadusafos Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157
  • Fenamiphos Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate,
  • Fipronil fluazinam, flucycloxuron, flucythrinate, flufenoxuron, flufenprox,
  • HCH heptenophos, hexaflumuron, hexythiazox, Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivemectin,
  • Methami dophos methidathione, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin,
  • Parathion A Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet,
  • Triazophos triazuron, trichlorfon, triflumuron, trimethacarb,
  • 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, emulsifiable concentrates, emulsions, foams, 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 itself into the soil. The seeds of the plants can also be treated.
  • the application rate can be varied over a wide range depending on the type of application.
  • the active substance concentrations in the treatment of parts of plants in the use forms are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.
  • amounts of active compound of 0.001 to 50 g per kg of seed, preferably 0.01 to 10 g are generally required.
  • active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% are required at the site of action.
  • reaction mixture was poured onto an ice-cold solution of 193.6 g (1.4 mol) of potassium carbonate in 1.75 l of water. It is mixed with ethyl acetate and suction filtered. When the organic phase is narrowed, further solid separates, which is likewise suctioned off. 355.1 g (95% of theory) of nicotinic acid 2,4-dichloroanilide are obtained.
  • Solvent 10 parts by weight of N-methyl-pyrrolidone 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 sprayed with a spore suspension of Leptosphaeria nodorum.
  • the plants remain in an incubation cabin at 20 ° C. and 100% relative atmospheric humidity for 48 hours.
  • the plants are placed in a greenhouse at a temperature of approx. 15 ° C and a relative humidity of approx. 80%.
  • Evaluation is carried out 10 days after the inoculation.
  • Example 1 shows an efficiency of 100% at an application rate of 250 g / ha, while the comparison substance (A) has an efficiency of 50%.
  • Emulsifier 0.3 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
  • the plants are then placed in a greenhouse at 23 to 24 ° C. and at a relative atmospheric humidity of approx. 75%.
  • Evaluation is carried out 10 days after the inoculation.
  • Spray liquor has an efficiency of 60% or more, while the comparison substance (A) has an efficiency of 37%.
  • Emulsifier 0.3 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
  • the plants are then placed in a greenhouse at 23 ° C. and a relative atmospheric humidity of approx. 70%.
  • Evaluation is carried out 10 days after the inoculation.
  • Spray liquor has an efficiency of more than 70%, while the comparison substance has no effect.
  • Emulsifier 0.3 part by weight of alkyl aryl polyglycol ether
  • the plants are then placed in a greenhouse at 23 to 24 ° C and at a relative humidity of approx. 75%.
  • Evaluation is carried out 10 days after the inoculation.
  • Eumulsifier 0.3 part by weight of alkyl aryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • the plants are then placed in a greenhouse at 23 ° C. and a relative atmospheric humidity of approx. 70%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
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  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Pyridine Compounds (AREA)

Abstract

Novel pyridine-3-imino alkyl esters of formula (I) in which R is methyl, ethyl n-propyl, n-butyl, sec. butyl, isobutyl, tert. butyl, pentyl, hexyl, heptyl, octyl, dodecyl or methoxy ethyl and R?1 and R2¿ are mutually independently fluorine, chorine, bromine, methyl, methoxy, trifluoromethyl or trifluoromethoxy, and their acid addition salts and metal salt complexes, a process for the production of the novel substances and their use as fungicides.

Description

PYRIDIN-3-IMIN0-ALKYLESTER ALS FUNGIZIDEPYRIDINE-3-IMIN0-ALKYLESTER AS A FUNGICIDE
Die vorliegende Errfindung betrifft neue Pyridin-3-imino-alkylester, ein Verfahren zu deren Herstellung und deren Verwendung als Fungizide.The present invention relates to new pyridine-3-imino-alkyl esters, a process for their preparation and their use as fungicides.
Es ist bereits bekannt, daß bestimmte Phenylimino-pyridin-Derivate fungizide Eigenschaften besitzen (vgl. EP-OS 0 008 145). So läßt sich z.B. 2',4'-It is already known that certain phenylimino-pyridine derivatives have fungicidal properties (cf. EP-OS 0 008 145). For example, 2 ', 4'-
Dichlorphenylimino-C-(isopropoxy)-methyl-3-pyridin zur Bekämpfung von Pilzen einsetzen. Die Wirksamkeit dieses Stoffes läßt aber bei niedrigen Aufwandmengen in manchen Fällen zu wünschen übrig.Use dichlorophenylimino-C- (isopropoxy) methyl-3-pyridine to combat fungi. The effectiveness of this substance leaves something to be desired in some cases at low application rates.
Es wurden nun neue Pyridin-3-iminoalkylester der FormelThere were now new pyridine-3-iminoalkyl esters of the formula
Figure imgf000003_0001
in welcher
Figure imgf000003_0001
in which
R für Methyl, Ethyl, n-Propyl, n-Butyl, sek.-Butyl, iso-Butyl, tert.-Butyl, Pentyl, Hexyl, Heptyl, Octyl, Dodecyl oder Methoxyethyl steht undR represents methyl, ethyl, n-propyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, dodecyl or methoxyethyl and
R1 und R2 unabhängig voneinander für Fluor, Chlor, Brom, Methyl, Methoxy, Trifluormethyl oder Trifluormethoxy stehen,R 1 and R 2 independently of one another represent fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl or trifluoromethoxy,
sowie deren Säureadditions-Salze und Metallsalz-Komplexe gefunden.as well as their acid addition salts and metal salt complexes.
Weiterhin wurde gefunden, daß man Pyridin-3-imino-alkylester der Formel (I) sowie deren Säureadditions-Salze und Metall salz-Komplexe erhält, wenn man Iminoverbindungen der Formel
Figure imgf000004_0001
Furthermore, it was found that pyridine-3-imino-alkyl esters of the formula (I) and their acid addition salts and metal salt complexes are obtained if imino compounds of the formula
Figure imgf000004_0001
in welcherin which
R1 und R2 die oben angegebenen Bedeutungen haben,R 1 and R 2 have the meanings given above,
mit Alkoholen der Formelwith alcohols of the formula
R-OH (πi)R-OH (πi)
in welcherin which
R die oben angegebene Bedeutung hat,R has the meaning given above,
gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Säurebindemittels umsetzt und an die so erhaltenen Verbindungen der Formel (I) gegebenenfalls anschließend eine Säure oder ein Metallsalz addiert.if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder and if appropriate an acid or a metal salt is then added to the compounds of the formula (I) thus obtained.
Schließlich wurde gefunden, daß die neuen Pyridin-3-imino-alkylester der Formel (I) sowie deren Säureadditions-Salze und Metallsalz-Komplexe sehr gute fungizide Eigenschaften besitzen.Finally, it was found that the new pyridine-3-imino-alkyl esters of the formula (I) and their acid addition salts and metal salt complexes have very good fungicidal properties.
Überraschenderweise zeichnen sich die erfmdungsgemäßen Stoffe durch eine wesentlich bessere fungizide Wirkung aus als die konstitutionell ähnlichsten, aus dem Stand der Technik bekannten Verbindungen gleicher Indikation. So übertref¬ fen die erfindungsgemäßen Stoffe z.B. das 2',4'-Dichlorphenylimino-C-(iso- propoxy)-methyl-3-pyridin, welches eine strukturell naheliegende Verbindung gleicher Wirkungsrichtung ist, bezüglich ihrer fungiziden Eigenschaften.Surprisingly, the substances according to the invention are distinguished by a substantially better fungicidal action than the most similar in terms of constitution, compounds of the same indication known from the prior art. Thus, the substances according to the invention exceed e.g. the 2 ', 4'-dichlorophenylimino-C- (isopropoxy) methyl-3-pyridine, which is a structurally obvious compound with the same direction of action, with regard to its fungicidal properties.
Die erfindungsgemäßen Pyridin-3-iminoalkylester sind durch die Formel (I) allge¬ mein definiert. R steht bevorzugt für Methyl, Ethyl, n-Propyl, n-Butyl, sek.-Butyl, iso-Butyl, tert.-Butyl, die Reste der FormelnThe pyridine-3-iminoalkyl esters according to the invention are generally defined by the formula (I). R preferably represents methyl, ethyl, n-propyl, n-butyl, sec-butyl, isobutyl, tert-butyl, the radicals of the formulas
-CH2CH2CH2CH2CH3, -CH(CH3)CH2CH2CH3, -CH(CH2CH3)2, -CH2CH2CH(CH3)2, -CH(CH3)CH(CH3)2, -C(CH3)2CH2CH3> -CH2CH(CH3)CH2CH3, -CH2C(CH3)3,-CH 2 CH 2 CH 2 CH 2 CH 3 , -CH (CH 3 ) CH 2 CH 2 CH 3 , -CH (CH 2 CH 3 ) 2 , -CH 2 CH 2 CH (CH 3 ) 2 , -CH ( CH 3 ) CH (CH 3 ) 2 , -C (CH 3 ) 2 CH 2 CH 3> -CH 2 CH (CH 3 ) CH 2 CH 3 , -CH 2 C (CH 3 ) 3 ,
-(CH2)5CH3, -CH(CH3)CH2CH2CH2CH3, -CH(CH2CH3)CH2CH2CH3,- (CH 2 ) 5 CH 3 , -CH (CH 3 ) CH 2 CH 2 CH 2 CH 3 , -CH (CH 2 CH 3 ) CH 2 CH 2 CH 3 ,
-CH2CH(CH3)CH2CH2CH3, -C(CH3)2CH2CH2CH3, -CH(CH2CH3)CH(CH3)2, -CH(CH3)CH2CH(CH3)2, -CH2CH2CH2CH(CH3)2, -CH2CH2CH(CH3)CH2CH3, -CH(CH3)CH(CH3)CH2CH3, -C(CH2CH3)2CH3, -CH(CH3)C(CH3)3, -C(CH3)2CH(CH3)2, -CH2CH2C(CH3)3. -CH2CH(CH2CH3)CH2CH3,-CH 2 CH (CH 3 ) CH 2 CH 2 CH 3 , -C (CH 3 ) 2 CH 2 CH 2 CH 3 , -CH (CH 2 CH 3 ) CH (CH 3 ) 2 , -CH (CH 3 ) CH 2 CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH (CH 3 ) 2 , -CH 2 CH 2 CH (CH 3 ) CH 2 CH 3 , -CH (CH 3 ) CH (CH 3 ) CH 2 CH 3 , -C (CH 2 CH 3 ) 2 CH 3 , -CH (CH 3 ) C (CH 3 ) 3 , -C (CH 3 ) 2 CH (CH 3 ) 2 , -CH 2 CH 2 C ( CH 3 ) 3 . -CH 2 CH (CH 2 CH 3 ) CH 2 CH 3 ,
-(CH2)6CH3, -CH(CH3)CH2CH2CH2CH2CH3, -CH(CH2CH3)CH2CH2CH2CH3,- (CH 2 ) 6 CH 3 , -CH (CH 3 ) CH 2 CH 2 CH 2 CH 2 CH 3 , -CH (CH 2 CH 3 ) CH 2 CH 2 CH 2 CH 3 ,
-C(CH3)2CH2CH2CH2CH3, -CH(CH2CH2CH3)CH(CH3)2; -CH(CH3)CH2CH2CH(CH3)2) -C(CH3)(CH2CH3)CH(CH3)2) -CH(CH2CH3)C(CH3)3, -CH[CH(CH3)2]2> -CH(CH3)CH2C(CH3)3, -C(CH2CH3)3,-C (CH 3 ) 2 CH 2 CH 2 CH 2 CH 3 , -CH (CH 2 CH 2 CH 3 ) CH (CH 3 ) 2; -CH (CH 3 ) CH 2 CH 2 CH (CH 3 ) 2) -C (CH 3 ) (CH 2 CH 3 ) CH (CH 3 ) 2) -CH (CH 2 CH 3 ) C (CH 3 ) 3 , -CH [CH (CH 3 ) 2 ] 2> -CH (CH 3 ) CH 2 C (CH 3 ) 3 , -C (CH 2 CH 3 ) 3 ,
-(CH2)7CH3, -CH(CH3)(CH2)5CH3> -CH(CH2CH3)(CH2)4CH3, -CH2CH(CH2CH3)CH2CH2CH2CH3, -CH(CH2CH3)CH(CH3)CH2CH2CH3,- (CH 2 ) 7 CH 3 , -CH (CH 3 ) (CH 2 ) 5 CH 3> -CH (CH 2 CH 3 ) (CH 2 ) 4 CH 3 , -CH 2 CH (CH 2 CH 3 ) CH 2 CH 2 CH 2 CH 3 , -CH (CH 2 CH 3 ) CH (CH 3 ) CH 2 CH 2 CH 3 ,
-CH(CH3)CH2CH2CH2CH(CH3)2, -CH2CH(CH2CH2CH3)2) -CH2CH(CH3)CH2C(CH3)3,-CH (CH 3 ) CH 2 CH 2 CH 2 CH (CH 3 ) 2 , -CH 2 CH (CH 2 CH 2 CH 3 ) 2) -CH 2 CH (CH 3 ) CH 2 C (CH 3 ) 3 ,
sowie füralso for
n-Dodecyl oder 2-Methoxy ethyl.n-dodecyl or 2-methoxy ethyl.
R1 steht bevorzugt für Fluor, Chlor, Brom, Methyl, Methoxy, Trifluormethyl oder Trifluormethoxy.R 1 preferably represents fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl or trifluoromethoxy.
R2 steht bevorzugt für Fluor, Chlor, Brom, Methyl, Methoxy, Trifluormethyl oder Trifluormethoxy.R 2 preferably represents fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl or trifluoromethoxy.
Bevorzugte erfindungsgemäße Stoffe sind auch Additionsprodukte aus Säuren und denjenigen Pyridin-3-imino-alkylestern der Formel (I), in denen R, R1 und R2 die oben als bevorzugt genannten Bedeutungen haben.Preferred substances according to the invention are also addition products of acids and those pyridine-3-iminoalkyl esters of the formula (I) in which R, R 1 and R 2 have the meanings given above as preferred.
Zu den Säuren, die addiert werden können, gehören vorzugsweise Halogenwas¬ serstoffsäuren, wie z.B. die Chlorwasserstoffsäure und die Bromwasserstoffsäure, insbesondere die Chlorwasser Stoff säure, ferner Phosphorsäure, Salpetersäure, Schwefelsäure, mono- und bifunktionelle Carbonsäuren und Hydroxycarbonsäuren, wie z.B. Essigsäure, Maleinsäure, Bernsteinsäure, Fumarsäure, Weinsäure, Zitro- nensäure, Salizylsäure, Sorbinsäure und Milchsäure sowie Sulfonsäuren, wie z.B. p-Toluolsulfonsäure, 1,5-Naphthalindisulfonsäure oder Camphersulfonsäure, und außerdem auch Saccharin und Thiosaccharin.The acids which can be added preferably include halohydric acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as acetic acid, maleic acid, Succinic acid, fumaric acid, tartaric acid, citric acid Nenoic acid, salicylic acid, sorbic acid and lactic acid as well as sulfonic acids such as p-toluenesulfonic acid, 1,5-naphthalenedisulfonic acid or camphorsulfonic acid, and also saccharin and thiosaccharin.
Außerdem bevorzugte erfindungsgemäße Stoffe sind Additionsprodukte aus Salzen von Metallen der II. bis IV. Haupt- und der I. und II. sowie IV. bis VIII. Neben¬ gruppe des Periodensystems der Elemente und Pyridin-3-imino-alkylestern der Formel (I), in denen R, R1 und R2 die oben als bevorzugt genannten Bedeutungen haben.In addition, preferred substances according to the invention are addition products from salts of metals of the II. To IV. Main group and of I. and II. And IV. To VIII. Subgroup of the periodic table of the elements and pyridine-3-imino-alkyl esters of the formula (I ), in which R, R 1 and R 2 have the meanings given above as preferred.
Hierbei sind Salze des Kupfers, Zinks, Mangans, Magnesiums, Zinns, Eisens und des Nickels besonders bevorzugt. Als Anionen dieser Salze kommen solche in Betracht, die sich von solchen Säuren ableiten, die zu physiologisch verträglichen Additionsprodukten führen. Besonders bevorzugte derartige Säuren sind in diesem Zusammenhang die Halogenwasserstoffsäuren, wie z.B. Chlorwasserstoffsäure und die Bromwasserstoffsäure, ferner Phosphorsäure, Salpetersäure und Schwefelsäure.Salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred. Anions of these salts are those which are derived from acids which lead to physiologically tolerable addition products. Particularly preferred such acids in this connection are the hydrohalic acids, e.g. Hydrochloric acid and hydrobromic acid, also phosphoric acid, nitric acid and sulfuric acid.
Als Beispiele für erfindungsgemäße Stoffe seien die in der folgenden Tabelle aufgeführten Pyridin-3-imino-alkylester genannt. Examples of substances according to the invention are the pyridine-3-imino-alkyl esters listed in the following table.
Tabelle 1Table 1
Figure imgf000007_0001
Figure imgf000007_0001
Figure imgf000007_0002
Tabelle 1 - Fortsetzung
Figure imgf000007_0002
Table 1 - continued
Figure imgf000008_0001
Tabelle 1 - Fortsetzung
Figure imgf000008_0001
Table 1 - continued
Figure imgf000009_0001
Tabelle 1 - Fortsetzung
Figure imgf000009_0001
Table 1 - continued
Figure imgf000010_0001
Tabelle 1 - Fortsetzung
Figure imgf000010_0001
Table 1 - continued
Figure imgf000011_0001
Tabelle 1 - Fortsetzung
Figure imgf000011_0001
Table 1 - continued
Figure imgf000012_0001
Tabelle 1 - Fortsetzung
Figure imgf000012_0001
Table 1 - continued
Figure imgf000013_0001
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000014_0001
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Figure imgf000015_0002
Figure imgf000015_0001
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Figure imgf000015_0002
Figure imgf000015_0001
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εzioo OΛV εzioo OΛV
Figure imgf000016_0001
Figure imgf000016_0001
Sunzjasyoj - \ ai BlSunzjasyoj - \ ai Bl
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Figure imgf000017_0001
gunzissuOii - i ajpqBi
Figure imgf000017_0001
gunzissuOii - i ajpqBi
SlSl
£ZZ,00/96 OΛV Tabelle 1 - Fortsetzung£ ZZ, 00/96 OΛV Table 1 - continued
Figure imgf000018_0001
Figure imgf000018_0001
Figure imgf000019_0002
Figure imgf000019_0001
Figure imgf000019_0002
Figure imgf000019_0001
-AI-AI
£ZZ.00/96 O . Tabelle 1 - Fortsetzung£ ZZ.00 / 96 O. Table 1 - continued
Figure imgf000020_0001
Tabelle 1 - Fortsetzung
Figure imgf000020_0001
Table 1 - continued
Figure imgf000021_0003
Figure imgf000021_0003
Verwendet man Pyridin-3-(2,4-dichlor-phenyl)-imino-chlorid und Pentan-3-ol als Ausgangsstoffe, so kann der Verlauf des erfindungsgemäßen Verfahrens durch das folgende Formelschema veranschaulicht werden:If pyridine-3- (2,4-dichlorophenyl) imino chloride and pentan-3-ol are used as starting materials, the course of the process according to the invention can be illustrated by the following formula:
Figure imgf000021_0001
Die bei der Durchführung des erfindungsgemäßen Verfahrens als Ausgangsstoffe benötigten Iminoverbindungen sind durch die Formel (II) allgemein definiert. In dieser Formel haben R1 und R2 vorzugsweise diejenigen Bedeutungen, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Stoffe der Formel (I) vorzugsweise für diese Substituenten genannt wurden.
Figure imgf000021_0001
Formula (II) provides a general definition of the imino compounds required as starting materials when carrying out the process according to the invention. In this formula, R 1 and R 2 preferably have those meanings which have already been mentioned preferably in connection with the description of the substances of the formula (I) according to the invention for these substituents.
Die Iminoverbindungen der Formel (II) sind bekannt oder lassen sich nach prinzipiell bekannten Verfahren herstellen (vgl. EP-OS 0 008 145). So erhält man Iminoverbindungen der Formel (II), indem man Nicotinsäureamide der FormelThe imino compounds of the formula (II) are known or can be prepared by processes which are known in principle (cf. EP-OS 0 008 145). Thus, imino compounds of the formula (II) are obtained by using nicotinamide of the formula
(IV)(IV)
Figure imgf000021_0002
in welcher
Figure imgf000021_0002
in which
R1 und R2 die oben angegebenen Bedeutungen haben,R 1 and R 2 have the meanings given above,
mit Thionylchlorid, gegebenenfalls in Gegenwart eines inerten Verdünnungs¬ mittels, wie Methylenchlorid oder 1,2-Dichlorethan, bei Temperaturen zwischen 10°C und 100°C umsetzt. Die Aufarbeitung erfolgt nach üblichen Methoden.with thionyl chloride, optionally in the presence of an inert diluent, such as methylene chloride or 1,2-dichloroethane, at temperatures between 10 ° C. and 100 ° C. The processing takes place according to usual methods.
Die Nicotinsäureamide der Formel (IV) sind bekannt oder lassen sich nach prinzipiell bekannten Methoden herstellen (vgl. EP-OS 0 008 145). So erhält man Nicotinsäureamide der Formel (IV), indem man Nicotinsäure der FormelThe nicotinamide of the formula (IV) are known or can be prepared by methods known in principle (cf. EP-OS 0 008 145). Nicotinic acid amides of the formula (IV) are obtained by using nicotinic acid of the formula
Figure imgf000022_0001
Figure imgf000022_0001
mit Thionylchlorid in Gegenwart von Pyridin bei Temperaturen zwischen 80°C und 120°C umsetzt und das dabei entstehende Zwischenprodukt anschließend mit Anilin-Derivaten der Formelwith thionyl chloride in the presence of pyridine at temperatures between 80 ° C and 120 ° C and then the resulting intermediate with aniline derivatives of the formula
Figure imgf000022_0002
Figure imgf000022_0002
in welcherin which
R1 und R2 die oben angegebenen Bedeutungen haben,R 1 and R 2 have the meanings given above,
gegebenenfalls in Gegenwart eines inerten organischen Verdünnungsmittels bei Temperaturen zwischen 80°C und 120°C umsetzt.optionally in the presence of an inert organic diluent at temperatures between 80 ° C and 120 ° C.
Die weiterhin bei der Durchführung des erfindungsgemäßen Verfahrens als Ausgangsstoffe benötigten Alkohole sind durch die Formel (III) allgemein definiert. In dieser Formel hat R vorzugsweise diejenigen Bedeutungen, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Stoffe der Formel (I) vorzugsweise für diesen Substituenten genannt wurden. Die Alkohole der Formel (III) sind allgemein bekannte Verbindungen der organischen Chemie.Formula (III) provides a general definition of the alcohols which are further required as starting materials when carrying out the process according to the invention. In this formula, R preferably has those meanings which have already been mentioned preferably for this substituent in connection with the description of the substances of the formula (I) according to the invention. The alcohols of the formula (III) are generally known compounds of organic chemistry.
Als Verdünnungsmittel kommen bei der Durchführung des erfindungsgemäßen Verfahrens alle für derartige Umsetzungen üblichen, inerten organischen Solventien in Betracht. Vorzugsweise verwendbar sind Ether, wie Diethylether,Suitable diluents for carrying out the process according to the invention are all inert organic solvents which are customary for such reactions. Ethers, such as diethyl ether, are preferably usable.
Methyl-tert.-butyl-ether, Ethylenglykol-dimethylether, Tetrahydrofuran und Dioxan, ferner Nitrile, wie Acetonitril, und außerdem gegebenenfalls halogenierte alipha- tische, cycloaliphatische und aromatische Kohlenwasserstoffe, wie Methylen¬ chlorid, Chloroform, Tetrachlorkohlenstoff, Hexan, Cyclohexan, Benzol, Toluol, Xylol und Chlorbenzol.Methyl tert-butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran and dioxane, also nitriles, such as acetonitrile, and also optionally halogenated aliphatic, cycloaliphatic and aromatic hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, hexane, cyclohexane, benzene , Toluene, xylene and chlorobenzene.
Als Säurebindemittel kommen bei der Durchführung des erfindungsgemäßen Verfahrens alle üblichen anorganischen oder organischen Basen in Frage. Vorzugsweise verwendbar sind Alkalimetall- oder Erdalkalimetall-hydroxide, -amide, -alkoholate, -carbonate und -hydrogencarbonate, wie Natriumhydroxid, Kaliumhydroxid, Natriumamid, Natriummethylat, Natriumethylat, Kalium-tert.- butylat, Natriumcarbonat, Kaliumcarbonat, Calciumcarbonat, Kaliumhydrogen- carbonat und Natriumhydrogencarbonat, und weiterhin tertiäre Amine, wie Tri- methylamin, Triethylamin, Tributylamin, N,N-Dimethylanilin, Pyridin, N-Methyl- piperidin, N,N-Dimethylaminopyridin, Diazabicyclooctan (DABCO), Diazabicyclo- nonen (DBN) oder Diazabicycloundecen (DBU).Suitable acid binders for carrying out the process according to the invention are all customary inorganic or organic bases. Alkali metal or alkaline earth metal hydroxides, amides, alcoholates, carbonates and hydrogen carbonates, such as sodium hydroxide, potassium hydroxide, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium carbonate, potassium carbonate, calcium carbonate, potassium hydrogen carbonate and Sodium bicarbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene ( DBU).
Die Reaktionstemperaturen können bei der Durchführung des erfindungsgemäßen Verfahrens innerhalb eines größeren Bereiches variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen -10°C und 120°C, vorzugsweise zwischen 0°C und 100°C.The reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures between -10 ° C and 120 ° C, preferably between 0 ° C and 100 ° C.
Bei der Durchführung des erfindungsgemäßen Verfahrens arbeitet man im allgemeinen unter Normaldruck. Es ist jedoch auch möglich, unter erhöhtem oder vermindertem Druck zu arbeiten.The process according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.
Bei der Durchführung des erfindungsgemäßen Verfahrens setzt man auf 1 Mol an Iminoverbindung der Formel (II) im allgemeinen 1 bis 2 Mol an Alkohol der Formel (III) sowie gegebenenfalls 1 Äquivalent oder auch einen Überschuß anWhen carrying out the process according to the invention, 1 to 2 mol of alcohol of the formula (III) and, if appropriate, 1 equivalent or else an excess are used per 1 mol of imino compound of the formula (II)
Säurebindemittel ein. Die Aufarbeitung erfolgt nach üblichen Methoden. Im allgemeinen geht man so vor, daß man das Reaktionsgemisch einengt, den Rückstand mit Wasser und einem mit Wasser wenig mischbaren organischen Lösungsmittel versetzt, die organische Phase abtrennt, nach gegebenenfalls vorherigem Trocknen einengt und den verbleibenden Rückstand gegebenenfalls durch Umkristallisation oder auf chromatographischem Wege weiter reinigt. Die Iminoverbindungen der Formel (II) können bei der Durchführung des erfindungs¬ gemäßen Verfahrens in Form von Hydrohalogeniden oder als freie Basen einge¬ setzt werden. In einer besonderen Variante des erfindungsgemäßen Verfahrens arbeitet man in der Weise, daß man Hydrohalogenide, z.B. Hydrochloride, von Iminoverbindungen der Formel (II) in einem geeigneten Solvens, z.B. Chloroform, suspendiert, durch anschließendes Behandeln mit wäßriger Alkalimetall-Base, z.B. wäßriger Natriumcarbonat-Lösung, in die freien Basen überführt und diese mit Alkoholen der Formel (HI) bzw. deren Salzen (Alkoholaten) gegebenenfalls in Gegenwart eines Phasentransfer-Katalysators umsetzt.Acid binder. The processing takes place according to usual methods. The general procedure is to concentrate the reaction mixture Water and a water-immiscible organic solvent are added to the residue, the organic phase is separated off, after drying, if appropriate, concentrated, and the remaining residue is optionally further purified by recrystallization or by chromatographic means. The imino compounds of the formula (II) can be used in the form of hydrohalides or as free bases when carrying out the process according to the invention. In a special variant of the process according to the invention, the process is carried out by suspending hydrohalides, for example hydrochlorides, of imino compounds of the formula (II) in a suitable solvent, for example chloroform, by subsequent treatment with aqueous alkali metal base, for example aqueous sodium carbonate. Solution, converted into the free bases and reacting these with alcohols of the formula (HI) or their salts (alcoholates), if appropriate in the presence of a phase transfer catalyst.
Die erfindungsgemäßen Pyridin-3-imino-alkylester der Formel (I) können in Säureadditions-Salze oder Metallsalz-Komplexe überführt werden.The pyridine-3-iminoalkyl esters of the formula (I) according to the invention can be converted into acid addition salts or metal salt complexes.
Zur Herstellung von Säureadditions-Salzen der Verbindungen der Formel (I) kommen vorzugsweise diejenigen Säuren in Frage, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Säureadditions-Salze als bevorzugte Säuren genannt wurden.For the preparation of acid addition salts of the compounds of formula (I), preference is given to those acids which have already been mentioned as preferred acids in connection with the description of the acid addition salts according to the invention.
Die Säureadditions-Salze der Verbindungen der Formel (I) können in einfacherThe acid addition salts of the compounds of formula (I) can in simpler
Weise nach üblichen Salzbildungsmethoden, z.B. durch Lösen einer Verbindung der Formel (I) in einem geeigneten inerten Lösungsmittel und Hinzufügen der Säure, z.B. Chlorwasserstoffsäure, erhalten werden und in bekannter Weise, z.B. durch Abfiltrieren, isoliert und gegebenenfalls durch Waschen mit einem inerten organischen Lösungsmittel gereinigt werden.Manner according to usual salt formation methods, e.g. by dissolving a compound of formula (I) in a suitable inert solvent and adding the acid, e.g. Hydrochloric acid can be obtained and in a known manner, e.g. by filtration, isolated and, if necessary, cleaned by washing with an inert organic solvent.
Zur Herstellung von Metallsalz-Komplexen der Verbindungen der Formel (I) kommen vorzugsweise diejenigen Salze von Metallen in Frage, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Metallsalz-Kom¬ plexe als bevorzugte Metallsalze genannt wurden.For the preparation of metal salt complexes of the compounds of the formula (I), preference is given to those salts of metals which have already been mentioned as preferred metal salts in connection with the description of the metal salt complexes according to the invention.
Die Metall salz-Kompl exe der Verbindungen der Formel (I) können in einfacherThe metal salt complications of the compounds of the formula (I) can be simplified
Weise nach üblichen Verfahren erhalten werden, so z.B. durch Lösen des Metallsalzes in Alkohol, z.B. Ethanol und Hinzufügen zu Verbindungen der Formel (I). Man kann Metallsalz-Komplexe in bekannter Weise, z.B. durch Abfiltrieren, isolieren und gegebenenfalls durch Umkristallisation reinigen.Can be obtained by conventional methods, for example by dissolving the metal salt in alcohol, for example ethanol and adding to compounds of Formula (I). Metal salt complexes can be isolated in a known manner, for example by filtering off, and optionally purified by recrystallization.
Die erfindungsgemäßen Wirkstoffe weisen eine starke mikrobizide Wirkung auf und können als Fungizide eingesetzt werden.The active compounds according to the invention have a strong microbicidal action and can be used as fungicides.
Fungizide werden im Pflanzenschutz eingesetzt zur Bekämpfung von Plasmodio- phoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.Fungicides are used in crop protection to combat Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.
Beispielhaft aber nicht begrenzend seien einige Erreger von pilzlichen und bakteriellen Erkrankungen, die unter die oben aufgezählten Oberbegriffe fallen, genannt:Some pathogens of fungal and bacterial diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:
Xanthomonas- Arten, wie Xanthomonas oryzae;Xanthomonas species, such as Xanthomonas oryzae;
Pseudomonas-Arten, wie Pseudomonas lachrymans;Pseudomonas species, such as Pseudomonas lachrymans;
Erwinia-Arten, wie Erwinia amylovora;Erwinia species, such as Erwinia amylovora;
Pythium-Arten, wie Pythium ultimum; Phytophthora- Arten, wie Phytophthora infestans;Pythium species, such as Pythium ultimum; Phytophthora species, such as Phytophthora infestans;
Pseudoperonospora-Arten, wie Pseudoperonospora humuli oder Pseudoperonospora cubensis;Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubensis;
Plasmopara-Arten, wie Plasmopara viticola;Plasmopara species, such as Plasmopara viticola;
Peronospora- Arten, wie Peronospora pisi oder P. brassicae; Erysiphe-Arten, wie Erysiphe graminis;Peronospora species, such as Peronospora pisi or P. brassicae; Erysiphe species, such as Erysiphe graminis;
Sphaerotheca-Arten, wie Sphaerotheca fuliginea;Sphaerotheca species, such as Sphaerotheca fuliginea;
Podosphaera-Arten, wie Podosphaera leucotricha;Podosphaera species, such as Podosphaera leucotricha;
Venturia-Arten, wie Venturia inaequalis;Venturia species, such as Venturia inaequalis;
Pyrenophora- Arten, wie Pyrenophora teres oder P. graminea; (Konidienform: Drechslera, Syn: Helminthosporium);Pyrenophora species, such as Pyrenophora teres or P. graminea; (Conidial form: Drechslera, Syn: Helminthosporium);
Cochliobolus-Arten, wie Cochliobolus sativus;Cochliobolus species, such as Cochliobolus sativus;
(Konidienform: Drechslera, Syn: Helminthosporium);(Conidial form: Drechslera, Syn: Helminthosporium);
Uromyces-Arten, wie Uromyces appendiculatus;Uromyces species, such as Uromyces appendiculatus;
Puccinia-Arten, wie Puccinia recondita; Tilletia-Arten, wie Tilletia caries;Puccinia species, such as Puccinia recondita; Tilletia species, such as Tilletia caries;
Ustilago-Arten, wie Ustilago nuda oder Ustilago avenae;Ustilago species, such as Ustilago nuda or Ustilago avenae;
Pellicularia-Arten, wie Pellicularia sasakii;Pellicularia species, such as Pellicularia sasakii;
Pyricularia-Arten, wie Pyricularia oryzae; Fusarium-Arten, wie Fusarium culmorum; Botrytis- Arten, wie Botrytis cinerea; Septoria-Arten, wie Septoria nodorum; Leptosphaeria- Arten, wie Leptosphaeria nodorum; Cercospora-Arten, wie Cercospora canescens;Pyricularia species, such as Pyricularia oryzae; Fusarium species, such as Fusarium culmorum; Botrytis species, such as Botrytis cinerea; Septoria species, such as Septoria nodorum; Leptosphaeria species, such as Leptosphaeria nodorum; Cercospora species, such as Cercospora canescens;
Alternaria-Arten, wie Alternaria brassicae; Pseudocercosporella-Arten, wie Pseudocercosporella herpotrichoides.Alternaria species, such as Alternaria brassicae; Pseudocercosporella species, such as Pseudocercosporella herpotrichoides.
Die gute Pflanzenverträglichkeit der Wirkstoffe in den zur Bekämpfung von Pflan¬ zenkrankheiten notwendigen Konzentrationen erlaubt eine Behandlung von ober- irdischen Pflanzenteilen, von Pflanz- und Saatgut und des Bodens.The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases allows treatment of above-ground parts of plants, of propagation stock and seeds and of the soil.
Die erfindungsgemäßen Wirkstoffe eignen sich insbesondere zur Bekämpfung von Pyricularia oryzae an Reis sowie zur Bekämpfung von Getreidekrankheiten, wie Leptosphaeria nodorum, Cochliobolus sativus, Pyrenophora teres und Erysiphe- Arten. Außerdem zeigen die erfindungsgemäßen Stoffe eine sehr gute Wirkung gegen Venturia, Uncinula, Sphaerotheca und Podosphaera.The active compounds according to the invention are particularly suitable for combating Pyricularia oryzae on rice and for combating cereal diseases, such as Leptosphaeria nodorum, Cochliobolus sativus, Pyrenophora teres and Erysiphe species. In addition, the substances according to the invention show a very good action against Venturia, Uncinula, Sphaerotheca and Podosphaera.
Die erfindungsgemäßen Stoffe können in die üblichen Formulierungen überführt werden, wie Lösungen, Emulsionen, Suspensionen, Pulver, Schäume, Pasten, Granulate, Aerosole, Feinstverkapselungen in polymeren Stoffen und in Hüllmassen für Saatgut, sowie ULV-Formulierungen. Diese Formulierungen werden in bekannter Weise hergestellt, z.B. durch Vermischen der Wirkstoffe mitThe substances according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV formulations. These formulations are made in a known manner, e.g. by mixing the active ingredients with
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, oder Alkylnaphthaline, chlorierte Aromaten oder chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chlorethylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, Alkohole, wie Butanol oder Glycol sowie deren Ether undExtenders, that is to say liquid solvents, liquefied gases and / or solid carriers under pressure, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and
Ester, Ketone, wie Aceton, Methylethylketon, Methylisobutylketon oder Cyclo- hexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethyl- sulfoxid, sowie Wasser; mit verflüssigten gasförmigen Streckmitteln oder Träger¬ stoffen sind solche Flüssigkeiten gemeint, welche bei normaler Temperatur und unter .Normaldruck gasförmig sind, z.B. Aerosol-Treibgase, wie Butan, Propan, Stickstoff und Kohlendioxid; als feste Trägerstoffe kommen in Frage: z.B. natür¬ liche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hoch- disperse Kieselsäure, Aluminiumoxid und Silikate; als feste Trägerstoffe fürEsters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water; Liquefied gaseous extenders or carriers mean liquids which are at normal temperature and are gaseous under normal pressure, for example aerosol propellants, such as butane, propane, nitrogen and carbon dioxide; The following are suitable as solid carriers: for example natural rock powder, such as kaolins, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates; as solid carriers for
Granulate kommen in Frage: z.B. gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehl, Kokosnußschalen, Maiskolben und Tabakstengel; als Emulgier- und/oder schaumerzeugende Mittel kommen in Frage: z.B. nichtionogene und anionische Emulgatoren, wie Polyoxyethylen-Fettsäure-Ester, Polyoxyethylen-Fett- alkohol-Ether, z.B. Alkylarylpolyglykol-Ether, Alkylsulfonate, Alkylsulfate, Aryl- sulfonate sowie Eiweißhydrolysate; als Dispergiermittel kommen in Frage: z.B. Lignin-Sulfitablaugen und Methylcellulose.Granules are possible: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foaming agents are possible: e.g. nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.
Es können in den Formulierungen Haftmittel wie Carboxy-methylcellulose, natür¬ liche und synthetische pulverige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospholipide, wie Kephaline und Lecithine, und synthetische Phospholipide. Weitere Additive können mineralische und vegetabile Öle sein.Adhesives such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.
Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid,Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide,
Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo- und Metallphthalo- cyaninfarb Stoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden.Ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc are used.
Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gewichts- prozent Wirkstoff, vorzugsweise zwischen 0,5 und 90 %.The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
Die erfindungsgemäßen Wirkstofe können bei der Anwendung als Fungizide als solche oder in ihren Formulierungen auch in Mischung mit bekannten Fungiziden, Bakteriziden, Akariziden, Nematiziden oder Insektiziden verwendet werden, um so z.B. das Wirkungsspektrum zu verbreitern oder Resistenzentwicklungen vorzu- beugen. In vielen Fällen erhält man dabei synergistische Effekte, d.h. dieWhen used as fungicides as such or in their 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. In many cases, synergistic effects are obtained, i.e. the
Wirksamkeit der Mischung ist größer als die Wirksamkeit der Einzelkomponenten.The effectiveness of the mixture is greater than the effectiveness of the individual components.
Als Mischpartner kommen beispielsweise die folgenden Stoffe in Frage: Fungizide:The following substances can be considered as mixing partners: Fungicides:
2-Aminobutan; 2-Anilino-4-methyl-6-cyclopropyl-pyrimidin; 2',6'-Dibromo-2-me- thyl-4'-trifluoromethoxy-4'-trifluorm ethyl- 1 ,3 -thiazol-5-carboxanilid; 2,6-Dichlor-N-2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide; 2,6-dichloro-N-
(4-trifluoromethylbenzyl)-benzamid; (E)-2-Methoxyimino-N-methyl-2-(2-phenoxy- phenyl)-acetamid; 8-Hydroxychinolinsulfat; Methyl-(E)-2-{2-[6-(2-cyanophenoxy)- pyrimidin-4-yloxy]-phenyl } -3 -methoxyacrylat; Methyl-(E)-methoximino [alpha-(o- tolyloxy)-o-tolyl]-acetat; 2-Phenylphenol (OPP), Aldimorph, Ampropylfos,(4-trifluoromethylbenzyl) benzamide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3 methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos,
Anilazin, Azaconazol,Anilazine, azaconazole,
Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,
Calciumpolysulfid, Captafol, Captan, Carbendazim, Carboxin, ChinomethionatCalcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate
(Quinomethionat), Chloroneb, Chloropicrin, Chlorothalonil, Chlozolinat, Cufraneb,(Quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb,
Cymoxanil, Cyproconazole, Cyprofuram,Cymoxanil, cyproconazole, cyprofuram,
Dichlorophen, Diclobutrazol, Diclofluanid, Diclomezin, Dicloran, Diethofencarb, Difenoconazol, Dimethirimol, Dimethomorph, Diniconazol, Dinocap, Diphenyl- amin, Dipyrithion, Ditalimfos, Dithianon, Dodine, Drazoxolon,Dichlorophen, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,
Edifenphos, Epoxyconazole, Ethirimol, Etridiazol,Edifenphos, epoxyconazole, ethirimol, etridiazole,
Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin,Fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin,
Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanil,Fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil,
Flutriafol, Folpet, Fosetyl-Aluminium, Fthalide, Fuberidazol, Furalaxyl,Flutriafol, folpet, fosetyl aluminum, fthalides, fuberidazole, furalaxyl,
Furmecyclox,Furmecyclox,
Guazatine,Guazatine,
Hexachlorobenzol, Hexaconazol, Hymexazol, Imazalil, Imibenconazol, Iminoctadin, Iprobenfos (IBP), Iprodion, Isoprothiolan,Hexachlorobenzene, hexaconazole, hymexazole, imazalil, imibenconazole, iminoctadine, Iprobefos (IBP), iprodione, isoprothiolan,
Kasugamycin, Kupfer-Zubereitungen, wie: Kupferhydroxid, Kupfernaphthenat,Kasugamycin, copper preparations, such as: copper hydroxide, copper naphthenate,
Kupferoxychlorid, Kupfersulfat, Kupferoxid, Oxin-Kupfer und Bordeaux- Mischung,Copper oxychloride, copper sulfate, copper oxide, oxine copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,
Nickel-dimethyldithiocarbamat, Nitrothal-isopropyl, Nuarimol,Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, Oxadixyl, Oxamocarb, Oxycarboxin,Ofurace, oxadixyl, oxamocarb, oxycarboxin,
Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin,Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin,
Probenazol, Prochloraz, Procymidon, Propamocarb, Propiconazole, Propineb, Pyrazophos, Pyrifenox, Pyrimethanil, Pyroquilon,Probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilone,
Quintozen (PCNB),Quintozen (PCNB),
Schwefel und Schwefel -Zubereitungen, Tebuconazol, Tecloftalam, Tecnazen, Tetraconazol, Thiabendazol, Thicyofen, Thiophanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazoxid, Trichlamid, Tricyclazol, Tridemorph, Triflumizol, Triforin, Triticonazol, Validamycin A, Vinclozolin,Sulfur and sulfur preparations, Tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, Thicyofen, thiophanate-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, validamycin A, vinclozolin,
Zineb, Ziram.Zineb, ziram.
Bakterizide:Bactericides:
Bronopol, Dichlorophen, Nitrapyrin, Nickel-Dimethyldithiocarbamat, Kasugamy- cin, Octhilinon, Furancarbonsäure, Oxytetracyclin, Probenazol, Streptomycin, Tecloftalam, Kupfersulfat und andere Kupfer-Zubereitungen.Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.
Insektizide / Akarizide / Nematizide:Insecticides / acaricides / nematicides:
Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alpha- methrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M,Abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb, alpha-methrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M,
Azocyclotin, Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyfluthrin,Azocyclotin, Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyfluthrin,
Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Buto- carboxin, Butylpyridaben,Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157
41 9, CGA 1 84699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin,41 9, CGA 1 84699, chloethocarb, chlorethoxyfos, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M, cis-resmethrin,
Clocythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin, Cyhalothrin,Clocythrin, clofentezin, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin,
Cyhexatin, Cypermethrin, Cyromazin,Cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron,Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron,
Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat,Diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflubenzuron, dimethoate,
Dimethylvinphos, Dioxathion, Disulfoton,Dimethylvinphos, dioxathione, disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox,Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox,
Ethoprophos, Etrimphos,Ethoprophos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate,Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate,
Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenprox,Fipronil, fluazinam, flucycloxuron, flucythrinate, flufenoxuron, flufenprox,
Fluvalinate, Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb,Fluvalinate, Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb,
HCH, Heptenophos, Hexaflumuron, Hexythiazox, Imidacloprid, Iprobenfos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivemectin,HCH, heptenophos, hexaflumuron, hexythiazox, Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivemectin,
Lamda-cyhalothrin, Lufenuron,Lamda-cyhalothrin, Lufenuron,
Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyd, Methacrifos,Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos,
Methami dophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,Methami dophos, methidathione, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin,
Naled, NC 184, NI 25, NitenpyramNaled, NC 184, NI 25, Nitenpyram
Omethoat, Oxamyl, Oxydemethon M, Oxydeprofos,Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet,Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet,
Phosphamdon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophos,Phosphamdon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophos,
Pyradaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen,Pyradaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen,
Quinalphos,Quinalphos,
RH 5992,RH 5992,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos, Tebufenozid, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin,Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos, Tebufenozid, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin,
Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb,Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb,
Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomethrin, Triarathen,Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomethrin, Triarathen,
Triazophos, Triazuron, Trichlorfon, Triflumuron, Trimethacarb,Triazophos, triazuron, trichlorfon, triflumuron, trimethacarb,
Vamidothion, XMC, Xylylcarb, Zetamethrin.Vamidothione, XMC, xylylcarb, zetamethrin.
Auch eine Mischung mit anderen bekannten Wirkstoffen, wie Herbiziden oder mitA mixture with other known active ingredients, such as herbicides or with
Düngemitteln und Wachstumsregulatoren ist möglich.Fertilizers and growth regulators are possible.
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder den daraus bereiteten Anwendungsformen wie gebrauchsfertige Lösungen, emulgierbare Kon¬ zentrate, Emulsionen, Schäume, Suspensionen, Spritzpulver, Pasten, lösliche Pul- ver, Stäubemittel und Granulate, angewendet werden. Die Anwendung geschieht in üblicher Weise, z.B. durch Gießen, Verspritzen, Versprühen, Verstreuen, Ver¬ stäuben, Verschäumen, Bestreichen usw. Es ist ferner möglich, die Wirkstoffe nach dem Ultra-Low- Volume- Verfahren auszubringen oder die Wirkstoffzuberei¬ tung oder den Wirkstoff selbst in den Boden zu injizieren. Es kann auch das Saat- gut der Pflanzen behandelt werden.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, emulsifiable concentrates, emulsions, foams, 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 itself into the soil. The seeds of the plants can also be treated.
Beim Einsatz der erfindungsgemäßen Stoffe kann die Aufwandmenge je nach Art der Applikation in einem größeren Bereich variiert werden. So liegen die Wirk- stoffkonzentrationen bei der Behandlung von Pflanzenteilen in den Anwendungs¬ formen im allgemeinen zwischen 1 und 0,0001 Gew.-%, vorzugsweise zwischen 0,5 und 0,001 %. Bei der Saatgutbehandlung werden im allgemeinen Wirkstoff¬ mengen von 0,001 bis 50 g je kg Saatgut, vorzugsweise 0,01 bis 10 g benötigt. Bei der Behandlung des Bodens sind Wirkstoffkonzentrationen von 0,00001 bis 0,1 Gew.-%, vorzugsweise von 0,0001 bis 0,02 %, am Wirkungsort erforderlich.When using the substances according to the invention, the application rate can be varied over a wide range depending on the type of application. Thus, the active substance concentrations in the treatment of parts of plants in the use forms are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%. In the case of seed treatment, amounts of active compound of 0.001 to 50 g per kg of seed, preferably 0.01 to 10 g, are generally required. When treating the soil, active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are required at the site of action.
Die Herstellung und die Verwendung der erfindungsgemäßen Stoffe geht aus den folgenden Beispielen hervor. The preparation and use of the substances according to the invention can be seen from the following examples.
HerstellungsbeispieleManufacturing examples
Beispiel 1example 1
Figure imgf000032_0001
Figure imgf000032_0001
6,0 g (0,2 mol) 80%iges Natriumhydrid werden in 290 ml 3-Pentanol durch 10- minütiges Rühren bei Raumtemperatur gelöst. Man gibt 42,8 g (0,15 mol) Pyridin-6.0 g (0.2 mol) of 80% sodium hydride are dissolved in 290 ml of 3-pentanol by stirring for 10 minutes at room temperature. 42.8 g (0.15 mol) of pyridine
3-(2,4-dichlor-phenyl)-imino-chlorid bei 0°C zu und rührt anschließend 16 Stunden bei Raumtemperatur. Danach engt man das Reaktionsgemisch durch Abziehen des Lösungsmittels unter vermindertem Druck ein. Der verbleibende Rückstand wird mit Wasser und Essigsäureethylester behandelt. Die organische Phase wird abge- trennt und durch Abziehen des Lösungsmittels unter vermindertem Druck ein¬ geengt. Der verbleibende Rückstand wird mit tert.-Butyl-methyletheπPetrolether = 1 :1 an Kieselgel chromatographiert. Durch Einengen des Eluates unter vermin¬ dertem Druck erhält man 25 g (49,4 % der Theorie) an Pyridin-3-(2,4-dichlor- phenyl)-imino-3 -pentyl-ester.3- (2,4-dichlorophenyl) imino chloride at 0 ° C and then stirred for 16 hours at room temperature. The reaction mixture is then concentrated by stripping off the solvent under reduced pressure. The remaining residue is treated with water and ethyl acetate. The organic phase is separated off and concentrated by drawing off the solvent under reduced pressure. The remaining residue is chromatographed on silica gel using tert-butyl-methylethene petrol ether = 1: 1. By concentrating the eluate under reduced pressure, 25 g (49.4% of theory) of pyridine-3- (2,4-dichlorophenyl) imino-3-pentyl ester are obtained.
1H-NMR-Spektrum (CDC13/TMS) 1 H-NMR spectrum (CDC1 3 / TMS)
5 = 1,004/1, 029/1,053 (6H); 1,757-1,874(4H); 5, 176/5, 196/5,216 (1H); 6,588/6,617 (1H); 7,017-7,053 (1H); 7,166-7,195 (1H); 7,211/7,268 (1H); 7,55-7,589 (1H); 8,544-8,593 (1H) 5 = 1.004 / 1, 029 / 1.053 (6H); 1.757-1.874 (4H); 5, 176/5, 196 / 5.216 (1H); 6.588 / 6.617 (1H); 7.017-7.053 (1H); 7.166-7.195 (1H); 7.211 / 7.268 (1H); 7.55 - 7.589 (1H); 8,544-8,593 (1H)
Herstellung von Ausgangssubstanzen:Production of starting substances:
Figure imgf000033_0001
Figure imgf000033_0001
Ein Gemisch aus 355,1 g (1,329 mol) Nicotinsäure-2,4-dichlor-anilid und 2214,8 g (18,62 mol) Thionylchlorid wird 2 Stunden unter Rückfluß erhitzt. Danach wird überschüssiges Thionylchlorid abdestilliert und der verbleibende Rückstand in Chloroform gelöst. Das entstehende Gemisch wird mehrfach mit eiskalter, wäßri¬ ger Natriumcarbonat-Lösung (insgesamt 184 g [1,736 Mol] Natriumcarbonat in 1,8 1 Wasser) ausgeschüttelt. Die organische Phase wird durch Abziehen des Lösungsmittels unter vermindertem Druck eingeengt. Man erhält auf diese Weise 379,6 g (100 % der Theorie) an Pyridin-3-(2,4-dichlor-phenyl)-imino-chlorid.A mixture of 355.1 g (1.329 mol) of nicotinic acid 2,4-dichloroanilide and 2214.8 g (18.62 mol) of thionyl chloride is heated under reflux for 2 hours. Excess thionyl chloride is then distilled off and the remaining residue is dissolved in chloroform. The resulting mixture is shaken out several times with ice-cold, aqueous sodium carbonate solution (a total of 184 g [1.736 mol] sodium carbonate in 1.8 l of water). The organic phase is concentrated by stripping off the solvent under reduced pressure. In this way, 379.6 g (100% of theory) of pyridine-3- (2,4-dichlorophenyl) imino chloride are obtained.
1H-NMR-Spektrum (CDC13/TMS) δ = 6,932/6,960 (1H); 7,265-7,319 (1H); 7,425-7,495 (2H); 8,416-8,456 (1H); 8,786-8,807 (1H); 9,387/9,394 (1H) ppm. 1 H NMR Spectrum (CDC1 3 / TMS) δ = 6.932 / 6.960 (1H); 7.265-7.319 (1H); 7.425-7.495 (2H); 8.416-8.456 (1H); 8,786-8,807 (1H); 9.387 / 9.394 (1H) ppm.
Figure imgf000033_0002
Figure imgf000033_0002
In ein Gemisch aus 172,2 g (1,4 Mol) Nicotinsäure und 221,2 g (2,8 Mol) Pyridin werden unter Rühren und Kühlung 166,6 g (1,4 Mol) Thionylchlorid so einge¬ tropft, daß die Temperatur des Gemisches 50°C nicht überschreitet. Nach been¬ deter Zugabe wird noch 1 Stunde auf 100°C erhitzt. Anschließend wird auf 30°C abgekühlt und bei dieser Temperatur unter Rühren mit 226,8 g (1,4 Mol) 2,4- Dichloranilin versetzt. Nach einstündigem Nachrühren bei 100°C wird das166.6 g (1.4 mol) of thionyl chloride are added dropwise to a mixture of 172.2 g (1.4 mol) of nicotinic acid and 221.2 g (2.8 mol) of pyridine with stirring and cooling so that the Temperature of the mixture does not exceed 50 ° C. After the addition has ended, the mixture is heated at 100 ° C. for 1 hour. The mixture is then cooled to 30 ° C. and 226.8 g (1.4 mol) of 2,4-dichloroaniline are added at this temperature with stirring. After stirring for one hour at 100 ° C
Reaktionsgemisch auf eine eiskalte Lösung von 193,6 g (1,4 Mol) Kaliumcarbonat in 1,75 1 Wasser gegossen. Man versetzt mit Essigester und saugt ab. Beim Ein¬ engen der organischen Phase scheidet sich weiterer Feststoff ab, der ebenfalls abgesaugt wird. Man erhält 355,1 g (95 % der Theorie) Nicotinsäure-2,4-dichlor- anilid. 1H-NMR-Spektrum (CDC13/TMS) δ = 7,482-7,519 (IH); 7,6-7,656 (2H); 7,751-7,759 (IH); 8,344-8,412 (IH); 8,797-8,854 (IH); 9,154-9,162 (IH); 10,424 (IH) ppm. The reaction mixture was poured onto an ice-cold solution of 193.6 g (1.4 mol) of potassium carbonate in 1.75 l of water. It is mixed with ethyl acetate and suction filtered. When the organic phase is narrowed, further solid separates, which is likewise suctioned off. 355.1 g (95% of theory) of nicotinic acid 2,4-dichloroanilide are obtained. 1 H NMR Spectrum (CDC1 3 / TMS) δ = 7.482-7.519 (IH); 7.6-7.656 (2H); 7,751-7,759 (IH); 8,344-8,412 (IH); 8,797-8,854 (IH); 9.154-9.162 (IH); 10.424 (IH) ppm.
Nach der zuvor angegebenen Methode werden auch die in der folgenden Tabelle 2 aufgeführten Verbindungen der Formel (I) hergestellt.The compounds of the formula (I) listed in Table 2 below are also prepared by the method given above.
Tabelle 2Table 2
Figure imgf000035_0001
Figure imgf000035_0001
Figure imgf000035_0002
Tabelle 2 (Fortsetzung)
Figure imgf000035_0002
Table 2 (continued)
Figure imgf000036_0001
Tabelle 2 (Fortsetzung)
Figure imgf000036_0001
Table 2 (continued)
Figure imgf000037_0001
Tabelle 2 (Fortsetzung)
Figure imgf000037_0001
Table 2 (continued)
Figure imgf000038_0001
Tabelle 2 (Fortsetzung)
Figure imgf000038_0001
Table 2 (continued)
Figure imgf000039_0001
Figure imgf000040_0001
Tabelle 2 (Tortsetzung)
Figure imgf000039_0001
Figure imgf000040_0001
Table 2 (goal setting)
Figure imgf000041_0001
Figure imgf000041_0001
VerwendungsbeispieleExamples of use
In den folgenden Verwendungsbeispielen wurde die Verbindung der nachstehend aufgeführten Formel als Vergleichssubstanz eingesetzt:In the following examples of use, the compound of the formula listed below was used as the reference substance:
Figure imgf000042_0001
(bekannt aus EP-OS 0 008 145).
Figure imgf000042_0001
(known from EP-OS 0 008 145).
Beispiel AExample A
Leptosphaeria nodorum-Test (Weizen) / protektivLeptosphaeria nodorum test (wheat) / protective
Lösungsmittel: 10 Gewichtsteile N-Methyl-pyrrolidon Emulgator: 0,6 Gewichtsteile AlkylarylpolyglykoletherSolvent: 10 parts by weight of N-methyl-pyrrolidone emulsifier: 0.6 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Ge¬ wichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of 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.
Zur Prüfung auf protektive Wirksamkeit besprüht man junge Pflanzen mit der Wirkstoffzubereitung in der angegebenen Aufwandmenge.To test for protective activity, young plants are sprayed with the active compound preparation in the stated application rate.
Nach Antrocknen des Spritzbelages werden die Pflanzen mit einer Sporen¬ suspension von Leptosphaeria nodorum besprüht. Die Pflanzen verbleiben 48 Stunden bei 20°C und 100 % relativer Luftfeuchtigkeit in einer Inkubationskabine.After the spray coating has dried on, the plants are sprayed with a spore suspension of Leptosphaeria nodorum. The plants remain in an incubation cabin at 20 ° C. and 100% relative atmospheric humidity for 48 hours.
Die Pflanzen werden in einem Gewächshaus bei einer Temperatur von ca. 15°C und einer relativen Luftfeuchtigkeit von ca. 80 % aufgestellt.The plants are placed in a greenhouse at a temperature of approx. 15 ° C and a relative humidity of approx. 80%.
10 Tage nach der Inokulation erfolgt die Auswertung.Evaluation is carried out 10 days after the inoculation.
In diesem Test zeigt die in dem Beispiel 1 aufgeführte erfindungsgemäße Verbin¬ dung bei einer Aufwandmenge von 250 g/ha einen Wirkungsgrad von 100 %, während die Vergleichssubstanz (A) einen Wirkungsgrad von 50 % aufweist. In this test, the compound according to the invention listed in Example 1 shows an efficiency of 100% at an application rate of 250 g / ha, while the comparison substance (A) has an efficiency of 50%.
Tabelle ATable A
Leptosphaeria nodorum-Test (Weizen) / protektivLeptosphaeria nodorum test (wheat) / protective
Figure imgf000044_0001
Figure imgf000044_0001
Beispiel BExample B
Sphaerotheca-Test (Gurke) / protektivSphaerotheca test (cucumber) / protective
Lösungsmittel: 4,7 Gewichtsteile AcetonSolvent: 4.7 parts by weight of acetone
Emulgator: 0,3 Gewichtsteile AlkylarylpolyglykoletherEmulsifier: 0.3 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Ge¬ wichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of 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.
Zur Prüfung auf protektive Wirksamkeit bespritzt man junge Pflanzen mit der Wirkstoffzubereitung bis zur Tropfnässe. Nach Antrocknen des Spritzbelages werden die Pflanzen mit Konidien des Pilzes Sphaerotheca fuliginea bestäubt.To test for protective effectiveness, young plants are sprayed with the preparation of active compound to runoff. After the spray coating has dried on, the plants are dusted with conidia of the fungus Sphaerotheca fuliginea.
Die Pflanzen werden anschließend bei 23 bis 24°C und bei einer relativen Luft¬ feuchtigkeit von ca. 75 % im Gewächshaus aufgestellt.The plants are then placed in a greenhouse at 23 to 24 ° C. and at a relative atmospheric humidity of approx. 75%.
10 Tage nach der Inokulation erfolgt die Auswertung.Evaluation is carried out 10 days after the inoculation.
In diesem Test zeigen die in den Beispielen 1 bis 7 aufgeführten erfϊndungsge- mäßen Stoffe bei einer einer Wirkstoffkonzentration von 25 ppm in derIn this test, the substances according to the invention listed in Examples 1 to 7 show an active substance concentration of 25 ppm in the
Spritzbrühe einen Wirkungsgrad von 60 % oder mehr, während die Vergleichs¬ substanz (A) einen Wirkungsgrad von 37 % aufweist. Spray liquor has an efficiency of 60% or more, while the comparison substance (A) has an efficiency of 37%.
Tabelle BTable B
Sphaerotheca-Test (Gurke) / protektivSphaerotheca test (cucumber) / protective
Figure imgf000046_0001
Tabelle B - Fortsetzung
Figure imgf000046_0001
Table B - continued
Figure imgf000047_0001
Tabelle B - Fortsetzung
Figure imgf000047_0001
Table B - continued
Figure imgf000048_0001
Figure imgf000048_0001
Beispiel CExample C
Podosphaera-Test (Apfel) / protektivPodosphaera test (apple) / protective
Lösungsmittel: 4,7 Gewichtsteile AcetonSolvent: 4.7 parts by weight of acetone
Emulgator: 0,3 Gewichtsteile AlkylarylpolyglykoletherEmulsifier: 0.3 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Ge¬ wichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of 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.
Zur Prüfung auf protektive Wirksamkeit bespritzt man junge Pflanzen mit der Wirkstoffzubereitung bis zur Tropfnässe. Nach Antrocknen des Spritzbelages werden die Pflanzen durch Bestäuben mit Konidien des Apfelmehltauerregers Podosphaera leucotricha inokuliert.To test for protective effectiveness, young plants are sprayed with the preparation of active compound to runoff. After the spray coating has dried on, the plants are inoculated by dusting with conidia of the pod mildew pathogen Podosphaera leucotricha.
Die Pflanzen werden dann im Gewächshaus bei 23 °C und einer relativen Luft¬ feuchtigkeit von ca. 70 % aufgestellt.The plants are then placed in a greenhouse at 23 ° C. and a relative atmospheric humidity of approx. 70%.
10 Tage nach der Inokulation erfolgt die Auswertung.Evaluation is carried out 10 days after the inoculation.
In diesem Test zeigen die in den Beispielen 1, 2, 4, 5 und 7 aufgeführten erfindungsgemäßen Stoffe bei einer Wirkstoffkonzentration von 25 ppm in derIn this test, the substances according to the invention listed in Examples 1, 2, 4, 5 and 7 show an active substance concentration of 25 ppm in the
Spritzbrühe einen Wirkungsgrad von mehr als 70 %, während die Vergleichs¬ substanz keine Wirkung aufweist. Spray liquor has an efficiency of more than 70%, while the comparison substance has no effect.
Tabelle CTable C.
Podosphaera-Test (Apfel) / protektivPodosphaera test (apple) / protective
Figure imgf000050_0001
Tabelle C - Fortsetzung
Figure imgf000050_0001
Table C - continued
Figure imgf000051_0001
Beispiel D
Figure imgf000051_0001
Example D
Sphaerotheca-Test (Gurke) / protektivSphaerotheca test (cucumber) / protective
Lösungsmittel: 4,7 Gew.-Teile AcetonSolvent: 4.7 parts by weight of acetone
Emulgator: 0,3 Gew.-Teile Alkyl-Aryl-PolyglykoletherEmulsifier: 0.3 part by weight of alkyl aryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gew.-To produce a suitable preparation of active compound, 1% by weight is mixed.
Teil Wirkstoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.Part of active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.
Zur Prüfung auf protektive Wirksamkeit werden junge Pflanzen mit der Wirkstoffzubereitung taufeucht besprüht. Nach Antrocknen des Spritzbelages werden die Pflanzen mit Kinidien des Pilzes Sphaerotheca fuliginea bestäubt.To test for protective efficacy, young plants are sprayed with the preparation of active compound as moist as dew. After the spray coating has dried on, the plants are dusted with kinidia of the fungus Sphaerotheca fuliginea.
Die Pflanzen werden anschließend bei 23 bis 24°C und bei einer relativen Luftfeuchtigkeit von ca. 75 % im Gewächshaus aufgestellt.The plants are then placed in a greenhouse at 23 to 24 ° C and at a relative humidity of approx. 75%.
10 Tage nach der Inokulation erfolgt die Auswertung.Evaluation is carried out 10 days after the inoculation.
Wirkstoffe, Wirkstoffkonzentrationen und Versuchsergebnisse gehen aus der folgenden Tabelle hervor. Active substances, active substance concentrations and test results are shown in the following table.
Tabelle DTable D
Sphaerotheca-Test (Gurke) / protektivSphaerotheca test (cucumber) / protective
Figure imgf000053_0001
Beispiel E
Figure imgf000053_0001
Example E
Podosphaera-Test (Apfel) / protektivPodosphaera test (apple) / protective
Lösungsmittel: 4,7 Gew.-Teile AcetonSolvent: 4.7 parts by weight of acetone
Eumulgator: 0,3 Gew.-Teile Alkyl-Aryl-PolyglykoletherEumulsifier: 0.3 part by weight of alkyl aryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of 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.
Zur Prüfung auf protektive Wirksamkeit werden junge Pflanzen mit der Wirkstoffzubereitung taufeucht besprüht. Nach Antrocknen des Spritzbelages werden die Pflanzen durch Bestäuben mit Konidien des Apfelmehltauerregers Podosphaera leucotrichia inokuliert.To test for protective efficacy, young plants are sprayed with the preparation of active compound as moist as dew. After the spray coating has dried on, the plants are inoculated by dusting with conidia of the pod mildew pathogen Podosphaera leucotrichia.
Die Pflanzen werden dann im Gewächshaus bei 23°C und einer relativen Luftfeuchtigkeit von ca. 70 % aufgestellt.The plants are then placed in a greenhouse at 23 ° C. and a relative atmospheric humidity of approx. 70%.
Wirkstoffe, Wirkstoffkonzentrationen und Versuchsergebnisse gehen aus der folgenden Tabelle hervor. Active substances, active substance concentrations and test results are shown in the following table.
Tabelle ETable E
Podosphaera-Test (Apfel) / protektivPodosphaera test (apple) / protective
Figure imgf000055_0001
Figure imgf000055_0001

Claims

PatentansprücheClaims
1. Pyridin-3-imino-alkylester der Formel1. Pyridin-3-imino-alkyl ester of the formula
Figure imgf000056_0001
Figure imgf000056_0001
in welcherin which
R für Methyl, Ethyl, n-Propyl, n-Butyl, sek.-Butyl, iso-Butyl, tert.- Butyl, Pentyl, Hexyl, Heptyl, Octyl, Dodecyl oder Methoxyethyl steht undR represents methyl, ethyl, n-propyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, dodecyl or methoxyethyl and
R1 und R2 unabhängig voneinander für Fluor, Chlor, Brom, Methyl, Methoxy, Trifluormethyl oder Trifluormethoxy stehen,R 1 and R 2 independently of one another represent fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl or trifluoromethoxy,
sowie deren Säureadditions-Salze und Metallsalz-Komplexe gefunden.as well as their acid addition salts and metal salt complexes.
2. Pyridin-3-imino-alkylester gemäß Anspruch 1, gekennzeichnet durch die Formel2. pyridine-3-imino-alkyl ester according to claim 1, characterized by the formula
Figure imgf000056_0002
Figure imgf000056_0002
Verfahren zur Herstellung von Pyridin-3-imino-alkylestern der FormelProcess for the preparation of pyridine-3-imino-alkyl esters of the formula
Figure imgf000056_0003
Figure imgf000056_0003
Figure imgf000056_0004
R für Methyl, Ethyl, n-Propyl, n-Butyl, sek.-Butyl, iso-Butyl, tert.- Butyl, Pentyl, Hexyl, Heptyl, Octyl, Dodecyl oder Methoxyethyl steht und
Figure imgf000056_0004
R represents methyl, ethyl, n-propyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, dodecyl or methoxyethyl and
R1 und R2 unabhängig voneinander für Fluor, Chlor, Brom, Methyl, Methoxy, Trifluormethyl oder Trifluormethoxy stehen,R 1 and R 2 independently of one another represent fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl or trifluoromethoxy,
sowie von deren Säureadditions-Salzen und Metallsalz-Komplexen, dadurch gekennzeichnet, daß man Iminoverbindungen der Formelas well as their acid addition salts and metal salt complexes, characterized in that imino compounds of the formula
Figure imgf000057_0001
in welcher
Figure imgf000057_0001
in which
R1 und R2 die oben angegebenen Bedeutungen haben,R 1 and R 2 have the meanings given above,
mit Alkoholen der Formelwith alcohols of the formula
R-OH (III)R-OH (III)
in welcherin which
R die oben angegebene Bedeutung hat,R has the meaning given above,
gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Säurebindemittels umsetzt und gegebenenfalls an die so erhaltenen Verbindungen der Formel (I) anschließend eine Säure oder ein Metallsalz addiert.if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder and if appropriate an acid or a metal salt is then added to the compounds of the formula (I) thus obtained.
4. Fungizide Mittel, gekennzeichnet durch einen Gehalt an mindestens einem Pyridin-3-imino-alkylester der Formel (I) gemäß Anspruch 1 bzw. an einem Säureadditions-Salz oder Metallsalz-Komplex eines Pyridin-3-imino-alkyl- esters der Formel (I). 5. Verwendung von Pyridin-3-imino-alkylestern der Formel (I) gemäß An¬ spruch 1 bzw. von deren Säureadditions-Salzen und Metallsalz-Komplexen zur Bekämpfung von Pilzen.4. Fungicidal agents, characterized by a content of at least one pyridine-3-imino-alkyl ester of the formula (I) according to claim 1 or an acid addition salt or metal salt complex of a pyridine-3-imino-alkyl ester of the formula (I). 5. Use of pyridine-3-imino-alkyl esters of the formula (I) according to claim 1 or of their acid addition salts and metal salt complexes for combating fungi.
6. Verfahren zur Bekämpfung von Pilzen, dadurch gekennzeichnet, daß man Pyridin-3-imino-alkylester der Formel (I) gemäß Anspruch 1 bzw. deren Säureadditions-Salze oder Metallsalz-Komplexe auf die Pilze und/oder deren Lebensraum ausbringt.6. A method of combating fungi, characterized in that pyridine-3-imino-alkyl esters of the formula (I) according to Claim 1 or their acid addition salts or metal salt complexes are applied to the fungi and / or their habitat.
7. Verfahren zur Herstellung von fungiziden Mitteln, dadurch gekennzeichnet, daß man Pyridin-3-imino-alkylester der Formel (I) gemäß Anspruch 1 bzw. deren Metallsalz-Komplexe oder Säureadditions-Salze mit Streckmitteln und/oder oberflächenaktiven Stoffen vermischt. 7. A process for the preparation of fungicidal agents, characterized in that pyridine-3-imino-alkyl esters of the formula (I) according to Claim 1 or their metal salt complexes or acid addition salts are mixed with extenders and / or surface-active substances.
PCT/EP1995/002323 1994-06-29 1995-06-16 Pyridine-3-imino alkyl esters as fungicides WO1996000723A1 (en)

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EP95924246A EP0767784A1 (en) 1994-06-29 1995-06-16 Pyridine-3-imino alkyl esters as fungicides
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Applications Claiming Priority (2)

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DEP4422763.9 1994-06-29
DE19944422763 DE4422763A1 (en) 1994-06-29 1994-06-29 Pyridin-3-imino alkyl ester

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0008145A2 (en) * 1978-08-08 1980-02-20 Shell Internationale Researchmaatschappij B.V. Use of phenyliminomethylpyridine derivatives as fungicides and plant growth regulants compositions containing such derivatives and phenyliminomethylpyridine derivatives and their preparation

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0008145A2 (en) * 1978-08-08 1980-02-20 Shell Internationale Researchmaatschappij B.V. Use of phenyliminomethylpyridine derivatives as fungicides and plant growth regulants compositions containing such derivatives and phenyliminomethylpyridine derivatives and their preparation

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