DE19517721A1 - Oxiranyl triazoles - Google Patents

Abstract

Disclosed are novel oxiranyl-triazoles of formula (I) in which: X stands for hydrogen, halogen, alkyl with 1-4 carbon atoms or alkoxy with 1-4 carbon atoms; Z stands for halogen, alkyl with 1-4 carbon atoms, alkyl halide with 1-4 carbon atoms and 1-5 halogen atoms, alkoxy with 1-4 carbon atoms, alkoxy halide with 1-4 carbon atoms and 1-5 halogen atoms, nitro, phenyl which has optionally been substituted once to three times identically or differently with a halogen; and m is 0, 1, 2 or 3. Also disclosed are the acid addition salts and metal salt complexes of the claimed diazoles, a process for producing them and their use as microbicides for the protection of plants and materials.

Description

The present invention relates to new oxiranyl triazoles, a process for their Production and their use as microbicides.

It has already become known that numerous azolyl-methyl-oxiranes and Hydroxyethyl azolyl derivatives have fungicidal properties (cf. EP-OS 0 327 913 and DE-OS 44 19 812). So z. B. 3,3-Dimethyl-2- (3- chlorophenyl) -2- (1,2,4-triazol-1-ylmethyl) oxirane and 2- (2-chlorophenyl) -3- (1- chlor-cyclopropyl) -3-hydroxy-4- (1,2,4-triazol-1-yl) -but-1-en to combat Use mushrooms. The effect of these substances is good, but leaves at low In some cases, application rates leave something to be desired.

There were now new oxiranyl triazoles of the formula

in which
X represents hydrogen, halogen, alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms,
Z for halogen, alkyl with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms and 1 to 5 halogen atoms, alkoxy with 1 to 4 carbon atoms, haloalkoxy with 1 to 4 carbon atoms and 1 to 5 halogen atoms, nitro or optionally single to triple, similar or phenyl substituted differently by halogen and
m represents the numbers 0, 1, 2 or 3,
as well as their acid addition salts and metal salt complexes.

The substances according to the invention contain two asymmetrically substituted ones Carbon atoms. They can therefore be in the form of diastereomers or optical Accumulate isomers. The present invention relates to both the individual Isomers as well as their mixtures.

It was also found that oxiranyl-triazoles of the formula (I) and their Acid addition salts and metal salt complexes are obtained when hydroxyethyl triazole derivatives of the formula

in which
X, Z and m have the meanings given above,
reacted with bases in the presence of a polar diluent and, if appropriate, then adding an acid or a metal salt to the compounds of the formula (I) thus obtained.

Finally, it was found that the new oxiranyl triazoles of the formula (I) and their acid addition salts and metal salt complexes very good microbicidal Have properties and both in crop protection and in Material protection can be used.  

Surprisingly, the substances according to the invention have a better one microbicidal activity as the most constitutionally similar, known Connections with a rich direction of action. So surpass those of the invention Substances that 3,3-dimethyl-2- (2-chlorophenyl) -2- (1,2,4-triazol-1-yl-methyl) -oxirane and the 2- (2-chlorophenyl) -3- (1-chloro-cyclopropyl) -3-hydroxy-4- (1,2,4-triazol-1-yl) -but- 1-s with regard to their fungicidal properties.

The oxiranyl triazoles according to the invention are general by the formula (I) Are defined.

X preferably represents hydrogen, fluorine, chlorine, methyl, ethyl, n-propyl, Isopropyl, methoxy and ethoxy.

Z preferably represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, iso propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, trichloromethyl, trifluor methyl, difluoromethyl, methoxy, ethoxy, trifluoromethoxy, difluoro methoxy, nitro or, if necessary, single or double, of the same type or phenyl differently substituted by fluorine and / or chlorine.

m is preferably the number 0, 1, 2 or 3. If m is 2 or 3 stands, Z can stand for the same or different residues.

Preferred substances according to the invention are also addition products from acids and those oxiranyl triazoles of the formula (I) in which X, Z and m are the have preferably indicated meanings.

The acids that can be added preferably include halogen water Substance acids, such as B. the hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, also phosphoric acid, nitric acid, Sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as B. acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, Citric acid, salicylic acid, sorbic acid and lactic acid as well as sulfonic acids, such as e.g. B. p-toluenesulfonic acid, 1,5-naphthalenedisulfonic acid, camphorsulfonic acid, Saccharin and thiosaccharin.  

Additionally preferred compounds according to the invention are addition products from salts of metals from II. to IV. main and I. and II. and IV. to VIII. Subgroup of the Periodic Table of the Elements and those oxiranyl triazoles of the formula (I) in which X, Z and m are those indicated as preferred Have meanings.

Here are salts of copper, zinc, manganese, magnesium, tin, iron and of nickel is particularly preferred. Anions of these salts are those in Be that derive from acids that are physiologically acceptable Lead addition products. Particularly preferred such acids are in this Connection the hydrohalic acids, such as. B. the hydrochloric acid and hydrobromic acid, further phosphoric acid, nitric acid and Schwe rock acid.

Examples of oxiranyl-triazoles of the formula (I) are those in the following Substances listed in the table.  

Table 1

If 2- (2-chlorophenyl) -3- (1-fluoro-cyclopropyl) -1,2-epoxy-4- (1,2,4- triazol-1-yl) -butan-3-ol as a starting material, sodium hydroxide as a base and a Methanol / water mixture as the reaction medium, the course of the  method according to the invention illustrated by the following formula will:

The starting materials in carrying out the process according to the invention Required hydroxyethyl triazole derivatives are general by the formula (II) Are defined. In this formula, X, Z and m preferably have those Meanings already related to the description of the Substances of the formula (I) according to the invention preferably for these radicals or for these Index.

Examples of hydroxyethyl triazole derivatives of the formula (II) are those in substances listed in the following table.  

Table 2

The hydroxyethyl triazole derivatives of the formula (II) are hitherto unknown. They can be prepared by using triazolyl-butenols of the formula

in which
X, Z and m have the meanings given above,
reacted with peracids in the presence of a diluent.

The in the manufacture of hydroxyethyl triazole derivatives of the formula (II) as Formula (III) generalizes triazolyl-butenols required as starting materials Are defined. In this formula, X, Z and m preferably have those Meanings already related to the description of the Substances of the formula (I) according to the invention preferably for these radicals or these Index.

The triazolyl-butenols of the formula (III) are known or can be reduced produce known methods in principle (cf. DE-OS 44 19 812).

Reaction components used in the production of hydroxyethyl triazole Derivatives of formula (II) according to the above procedure all for such Conversions usual peracids into consideration. Are preferably usable Perbenzoic acid, 3-chloro-perbenzoic acid and peracetic acid.

Diluents used in the production of hydroxyethyl triazole Derivatives of formula (II) according to the above procedure all for such Implementation of the usual inert, organic solvents. Preferably Halogenated aliphatic hydrocarbons such as methylene can be used  chloride, chloroform or carbon tetrachloride and also aliphatic Carboxylic acids, such as acetic acid or glacial acetic acid.

The reaction temperatures in the production of hydroxyethyl triazole Derivatives of formula (II) according to the above method within a certain Range can be varied. Generally one works at temperatures between -20 ° C and + 60 ° C, preferably between 0 ° C and 40 ° C.

In the preparation of hydroxyethyl triazole derivatives of the formula (II) according to the The above procedure is generally carried out under normal pressure. But it is also possible to work under increased or reduced pressure.

In the preparation of hydroxyethyl triazole derivatives of the formula (II) according to the The above process is based on 1 mol of triazolyl-butenol of the formula (III) in generally 1 to 5 moles, preferably 1.2 to 2 moles of peracid. The Refurbishment is carried out using customary methods. In general, this is how that the reaction mixture is mixed with water, several times with one Water miscible organic solvent extracted, the combined organic phases in succession with aqueous alkaline solution and aqueous Washes sodium thiosulfate solution, then dries and concentrates. The remaining one Residue can optionally by conventional methods such. B. by Chromatography or recrystallization of any that may be present Impurities are freed.

All come as bases when carrying out the process according to the invention for such reactions, the usual alkaline substances are considered. Alkali and alkaline earth metal hydroxides such as Lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, further Alkali and alkaline earth metal carbonates and bicarbonates, such as sodium carbonate, potassium carbonate, calcium carbonate and sodium hydrogen carbonate, and also organic bases, such as trimethylamine, triethylamine, tributylamine, N, N- Dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diaza bicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).  

Suitable diluents for carrying out the process according to the invention Process polar organic solvents, optionally in a mixture with water in question. Alcohols such as methanol, ethanol, Propanol, isopropanol, n-butanol and tert-butanol, optionally in a mixture with water.

The reaction temperatures can be carried out when carrying out the process according to the invention Process can be varied within a wide range. In general one works at temperatures between 0 ° C and 100 ° C, preferably between 20 ° C and 90 ° C.

When carrying out the method according to the invention one works in general under normal pressure. But it is also possible to increase or to work under reduced pressure.

When carrying out the process according to the invention, the starting point is 1 mol Hydroxyethyl-triazole derivative of the formula (II) in general 1 to 4 mol, preferably 1.5 to 3 moles of base. The processing takes place according to usual Methods. In general, the procedure is followed in that the reaction mixture Water added, several times with an organic that is not very miscible with water Solvent extracted, the combined organic phases dried and concentrated. The remaining residue can by conventional methods, for. B. by Chromato graphy or recrystallization of any impurities be freed.

The oxiranyl-triazoles of the formula (I) according to the invention can be added in acid Salts or metal salt complexes are transferred.

For the preparation of acid addition salts of the compounds of the formula (I) those acids that are already related are preferred with the description of the acid addition salts according to the invention as preferred Acids were called.

The acid addition salts of the compounds of formula (I) can in simpler Way according to usual salt formation methods, e.g. B. by loosening a connection of formula (I) in a suitable inert solvent and adding the  Acid, e.g. As hydrochloric acid can be obtained and in a known manner, for. B. by filtration, isolated and optionally by washing with an inert organic solvents can be cleaned.

For the preparation of metal salt complexes of the compounds of the formula (I) are preferably those salts of metals that are already in the Connection with the description of the metal salt grain according to the invention plexes were mentioned as preferred metal salts.

The metal salt complexes of the compounds of formula (I) can in simpler Be obtained by conventional methods, such. B. by solving the Metal salt in alcohol, e.g. B. ethanol and adding to compounds of Formula (I). You can metal salt complexes in a known manner, for. B. by Filter off, isolate and if necessary clean by recrystallization.

The active compounds according to the invention have a strong microbicidal action and can be used to combat unwanted microorganisms such as fungi and Bacteria can be used in crop protection and material protection.

Fungicides are used in crop protection to combat Plasmodio phoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

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 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;
(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 good plant tolerance of the active ingredients in the fight against Concentrations necessary for plant diseases allow treatment of above-ground parts of plants, of seedlings and soil.

The active compounds according to the invention are particularly suitable for combating Pyricularia oryzae and Pellicularia sasakii on rice and for combating Cereal diseases such as Leptosphaeria nodorum, Cochliobolus sativus, Pyreno phora teres, Pseudocercosporella herpotrichoides, Erysiphe and Fusarium species. In addition, the substances according to the invention show a very good and broad in vitro Effect.

In material protection, the substances according to the invention can be used to protect technical materials against infestation and destruction by unwanted Use microorganisms.  

In the present context, technical materials include non-living ones Understand materials prepared for use in engineering have been. For example, technical materials made by Active substances according to the invention against microbial change or destruction to be protected, adhesives, glues, paper and cardboard, textiles, leather, Wood, paints and plastic articles, cooling lubricants and others Materials that can be attacked or decomposed by microorganisms. Parts of production are also part of the materials to be protected plants, for example cooling water circuits, which are produced by increasing Microorganisms can be affected. As part of the present Er As technical materials, adhesives, glues and papers are preferred and cartons, leather, wood, paints, coolants and Heat transfer liquids called, particularly preferably wood.

As microorganisms that break down or change the technical Materials can cause, for example, bacteria, fungi, yeast, algae and called mucus organisms. The ones according to the invention preferably act Active ingredients against fungi, in particular mold, wood-staining and wood destructive fungi (Basidiomycetes), as well as against mucus organisms and algae.

For example, microorganisms of the following genera may be mentioned:
Alternaria, such as Alternaria tenuis,
Aspergillus, such as Aspergillus niger,
Chaetomium, like Chaetomium globosum,
Coniophora, such as Coniophora puteana,
Lentinus, such as Lentinus tigrinus,
Penicillium, such as Penicillium glaucum,
Polyporus, such as Polyporus versicolor,
Aureobasidium, such as Aureobasidium pullulans,
Sclerophoma, such as Sclerophoma pityophila,
Trichoderma, like Trichoderma viride,
Escherichia, such as Escherichia coli,
Pseudomonas, such as Pseudomonas aeroginosa,
Staphylococcus, such as Staphylococcus aureus.

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 envelopes masses for seeds as well as ULV formulations.

These formulations are prepared in a known manner, e.g. B. by Mixing the active ingredients with extenders, i.e. liquid solvents, under Pressurized liquefied gases and / or solid carriers, if necessary using surface-active agents, ie emulsifiers and / or Dispersing agents and / or foaming agents. In case of use of water as an extender can e.g. B. also organic solvents Auxiliary solvents can be used. As liquid solvents come in essential in question: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as Chlorobenzenes, chlorethylene or methylene chloride, aliphatic carbons Hydrogen, such as cyclohexane or paraffins, e.g. B. petroleum fractions, alcohols, such as Butanol or glycol and their ethers and esters, ketones, such as acetone, Methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solution agents such as dimethylformamide and dimethyl sulfoxide, and water; with ver liquid gaseous extenders or carriers are such liquids meant which are gaseous at normal temperature and pressure, e.g. B. aerosol propellants such as butane, propane, nitrogen and carbon dioxide; as fixed Carriers come into question: z. B. natural stone 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 come into question: z. B. broken chene and fractionated natural rocks such as calcite, marble, pumice, sepiolite, Dolomite and synthetic granules from inorganic and organic flours as well as granules of organic material such as sawdust, coconut shells, corn pistons and tobacco stems; as an emulsifier and / or foam-generating agent come into question: z. B. non-ionic and anionic emulsifiers, such as poly oxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. Alkylaryl poly glycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as dispersants come into question: z. B. lignin sulfite and methyl cellulose.  

In the formulations, adhesives such as carboxymethylcellulose, naturally Liche and synthetic powdery, granular or latex-shaped polymers used such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural Phospholipids such as cephalins and lecithins, and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, Copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 weight percent active ingredient, preferably between 0.5 and 90%.

When used in crop protection, the active compounds according to the invention can be used as such or in their formulations also in a mixture with known fungicides, Bactericides, acaricides, nematicides or insecticides can be used so e.g. B. to broaden the spectrum of activity or develop resistance to prevent. In some cases, synergistic effects also occur means that the mixture has a higher effect than the sum of the Effects of the individual components.

As a mixing partner come z. B. Consider the following substances:

Fungicides

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine: 2 ′, 6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxani-lid ; 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoximino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2 - {(2- [6- (2-cyanophen oxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl- (E) methoximino [alpha- (o-tolyloxy ) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,
Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,
Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,
Dichlorophen, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithlon, ditalimfos, dithianon, dodine, drazoxolone,
Edifenphos, epoxyconazole, ethirimol, etridiazole,
Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fen propimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanyl, Futuberolosil, Futuberfosil , Furmecyclox,
Guazatine,
Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodione, Isoprothiolan,
Kasugamycin, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,
Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, oxadixyl, oxamocarb, oxycarboxin,
Pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyr azophos, pyrifenox, pyrimethanil, pyroquilon,
Quintozen (PCNB),
Sulfur and sulfur preparations,
Tebuconazole, tecloftalam, tecnazene, tetraconazole, Thlabendazol, Thicyofen, thiophanate-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
Validamycin A, vinclozoiin,
Zineb, ziram.

Bactericides

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, Octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, Teclofta lam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides

Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alpha methrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,
Bacillus thuringiensis, 4-bromo-2- (4-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacyfluorine, bifenthrin, BPMC, brofenprox , Bromophos A, Bufencarb, Buprofezin, Buto carboxin, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184 699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrinothrinhrhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrofhrinhrinhrinhrinhrofhrinothrinhrhrinhrinhrhrinhrinhrofhrinothrinophrinothrinophrinothrinothrinophrinothrinophrinothrinophrinophrine , Cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethopro phos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenothxinfox, Fufionophon, Fufionophon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufon
HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,
Lambda cyhalothrin, lufenuron,
Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Metamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
Naled, NC 184, M 25, Nitenpyram,
Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophhine, Pyrachlophhion, Pyrachlophion, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophion Pyridaben, pyrimidifen, pyriproxifen,
Quinalphos,
RH 5992,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozide, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos, Tetbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomenhriazononium, Tralomenhriazonium, Tronomenhrononium, Tronomenhrononium
Vamidothione, XMC, xylylcarb, zetamethrin.

A mixture with other known active ingredients, such as herbicides or with Fertilizers and growth regulators are possible.

The active substances can be used as such, in the form of their formulations or in the form thereof prepared application forms such as ready-to-use solutions, suspensions, Wettable powders, pastes, soluble powders, dusts and granules will. The application is done in the usual way, e.g. B. by pouring, Spraying, spraying, scattering, dusting, foaming, brushing, etc. It is also possible to use the active ingredients according to the ultra-low-volume method apply or the drug preparation or the drug itself in the Inject soil. The seeds of the plants can also be treated.

When treating parts of plants, the active substance concentrations can be in the application forms can be varied over a wide range. They are in the generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.

In the seed treatment, amounts of active ingredient are generally from 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g.

When treating the soil, active ingredient concentrations are from 0.00001 to 0.1 wt .-%, preferably from 0.0001 to 0.02 wt .-% required at the site of action Lich.  

The means used to protect technical materials contain the Active ingredients in general in an amount of 1 to 95%, preferably from 10 to 75%.

The application concentrations of the active compounds according to the invention are directed according to the type and the occurrence of the microorganisms to be controlled and according to the composition of the material to be protected. The optimal use quantity can be determined by test series. In general, the Application concentrations in the range of 0.001 to 5 wt .-%, preferably from 0.05 to 1.0% by weight, based on the material to be protected.

The effectiveness and spectrum of activity of the material according to the invention active ingredients to be used for protection or the agents that can be produced from them, Concentrates or more generally formulations can be increased if optionally further antimicrobial compounds, fungicides, Bactericides, herbicides, insecticides or other agents to enlarge the Spectrum of effects or achieving special effects such. B. the additional Protection against insects can be added. These blends can be a broader one Spectrum of activity than the compounds of the invention. In many In this case, synergistic effects are obtained, i. H. the effectiveness of the mixture is greater than the effectiveness of the individual components.

The production and use of substances according to the invention illustrated by the following examples.  

Manufacturing examples example 1

A solution of 0.5 g (1.5 mmol) of 2- (2-chlorophenyl) -3- (1-fluoro-cyclopropyl) -1,2- epoxy-4- (1,2,4-triazol-1-yl) butan-3-ol in 10 ml of a mixture of 4 parts Methanol and 1 part of water are mixed with 0.12 g (3 mmol) of sodium hydroxide and heated under reflux for 2 hours. Then the reaction mixture with Water was added and the mixture was extracted several times with ethyl acetate. The United organic phases are dried over sodium sulfate and then under reduced pressure. The remaining residue is washed with acetic acid ethyl ester: cyclohexane = 2: 1 as eluent, chromatographed on silica gel.

After concentrating the eluate under reduced pressure, 0.3 g (60% of theory) of 2- (2-chlorophenyl) -3- (1-fluorocydopropyl) -2,3-epoxy-4- ( 1,2,4-triazol-1-yl) butan-1-ol.
1 H-NMR spectrum (200 MHz, CDCl₃, TMS)
δ = 0.1-0.4 (m, 2H); 0.5-0.7 (m, 1H); 0.8-1.0 (m, 2H); 4.0-4.3 (m. 2H); 4.77 (d, J = 15 Hz); 4.99 (d, J = 15 Hz); 5.09 (d, J = 1 Hz); 5.1 (d) J = 1 Hz, together 2H); 7.1-7.45 (m, 4H); 8.01 (s); 8.1 (s); 8.28 (s, together 2H) ppm.

Manufacture of starting substances

A solution of 5 g (17 mmol) of 2- (2-chlorophenyl) -3- (1-fluoro-cyclopropyl) -3-hydroxy-4- (1,2,4-triazol-1-yl) -but 8 g (23 mmol) of 3-chloro-perbenzoic acid are added to -1-ene in 100 ml of dichloromethane and the mixture is stirred at room temperature for 15 hours. Then the reaction mixture is mixed with water and extracted several times with dichloromethane. The combined organic phases are washed first with aqueous sodium carbonate solution and then with 5% by weight aqueous sodium thiosulfate solution. After drying over sodium sulfate, the organic phase is concentrated under reduced pressure. The remaining residue is chromatographed on silica gel using ethyl acetate: cyclohexane = 2: 1 as the eluent. By concentrating the eluate, 3.6 g (65% of theory) of 2- (2-chlorophenyl) -3- (1-fluoro-cyclopropyl) -1,2-epoxy-4- (1,2,4- triazol-1-yl) butan-3-ol.
1 H-NMR spectrum (200 MHz, CDCl₃, TMS)
δ = 0.1-0.5 (m, 2H); 0.7-1.0 (m, 2H); 2.9-3.1 (m, 1H); 3.59 (d, J = 4 Hz); 3.67 (d, J = 4 Hz, together 1H); 4.08 (s, 1H); 4.21 (d, J = 13 Hz); 4.6 (d, J = 13 Hz; together 1H); 4.88 (d, J = 13 Hz); 5.0 (d, J = 13 Hz, together 1H); 7.2-7.7 (m, 4H); 7.98 (s); 8.0 (s, together 1H); 8.11 (s); 8.13 (s, together 1H) ppm.

A solution of 6.2 g (22 mmol) of 1-chloro-2- (1-fluorocyclopropyl) -3- (2-chlorophenyl) but-3-en-2-ol, 5.2 g (75 mmol) 1 , 2,4-triazole and 3.4 g (30 mmol) of potassium tert-butoxide in 50 ml of dimethylformamide are stirred at 80 ° C. for 8 hours. The reaction mixture is then concentrated by removing the solvent under reduced pressure. The remaining residue is taken up in ethyl acetate, washed with water, the organic phase is dried over sodium sulfate and concentrated by stripping off the solvent under reduced pressure. The remaining residue is chromatographed on silica gel using ethyl acetate: cyclohexane = 2: 1 as the eluent. Concentration of the eluate gives 0.7 g (10% of theory) of 2- (2-chlorophenyl) -3- (1-fluorocyclopropyl) -3-hydroxy- 4- (1,2,4-triazole-1- yl) -but-1-en.
1 H-NMR spectrum (200 MHz, CDCl₃, TMS)
δ = 0.2-0.5 (m, 2H); 0.75-0.95 (m, 2H); 4.43 (d, J = 14 Hz, 1H); 4.9 (d, J = 14 Hz, 1H); 5.36 (d, J = 2 Hz, 1H); 5.65 (d, J = 2 Hz, 1H); 7.3-7.8 (m, 4H); 8.0 (s. 1H); 8.22 (s, 1H) ppm.

A solution of 5.0 g (25 mmol) of α-bromo-2-chlorostyrene in 10 ml of absolute Diethyl ether is made under an argon atmosphere and with stirring at room temperature in a mixture of 0.85 g (35 mmol) magnesium shavings and 10 diethyl ether dropped in. When the addition is complete, the reaction mixture is kept under for 1 hour Reflux heated. The Grignard solution thus obtained is at room temperature with stirring in a solution of 3.8 g (28 mmol) of 1-fluorocyclopropyl chloromethyl ketone added dropwise in 10 ml of diethyl ether. When the addition is complete, it will The mixture was heated under reflux for a further 4 hours. Then you move that Reaction mixture with saturated, aqueous ammonium chloride solution, that pours resulting mixture on water and extracted several times with diethyl ether. The combined organic phases are washed with saturated, aqueous sodium chloride Solution washed and after drying over sodium sulfate by stripping of the solvent concentrated under reduced pressure. 6.2 g (90% of theory) on 1-chloro-2- (1-fluorocyclopropyl) -3- (2-chlorophenyl) but-3-en-2-ol.  

According to the method given in Example 1, those in the following Table 3 substances of formula (II) prepared.

Table 3

Example 2

δ = 0.2-1.0 (m, 4H); 2.94 (d, J = 5 Hz); 3.06 (d, J = 4 Hz, together 1H); 3.39 (d, J = 4 Hz); 3.61 (d, J = 5 Hz, together 1H); 4.27 (d, J = 14 Hz); 4.52 (d, J = 15 Hz, together 1H); 4.86 (d, J = 15 Hz); 5.08 (d, J = 14 Hz, together 1H); 5.3 (s, 1H); 7.0-7.65 (m, 4H); 8.0 (s); 8.01 (s, total 1); 8.34 (s, 1H) ppm.  

Example 3

δ = 0.1-1.0 (m, 4H); 2.5 (d, J = 4 Hz); 2.65 (d, J = 4 Hz); 2.78 (d, J = 5 Hz); 3.35 (d, J = 5 Hz, together 2H); 4.3-4.75 (m, 2H); 7.2-7.7 (m, 4H); 7.98 (s); 8.0 (s, together 1H); 8.08 (s); 8.21 (s, together 1H) ppm.

Example 4

δ = 0.1-0.8 (m, 4H); 2.83 (d, J = 5 Hz); 3.0 (d, J = 4 Hz, together 1H); 3.12 (d, J = 4 Hz); 3.4 (d, J = 5 Hz, together 1H); 4.13 (d, J = 15 Hz); 4.56 (d, J = 14 Hz, together 1H); 4.2 (s. 1H); 4.76 (d, J = 14 Hz); 4.98 (d, J = 15 Hz, together 1H); 7.2-7.8 (m, 5H); 7.92 (s); 8.02 (s, total 1H); 8.27 (s); 8.42 (s, together 1H) ppm.

Example 5

δ = 0.1-1.0 (m, 4H); 2.73 (d, 5Hz); 2.97 (d, J = 4 Hz, together 1H); 3.11 (d, J = 4 Hz); 3.3 (d, J = 5 Hz, together 1H); 4.12 (dd, J = 15 and 5 Hz); 4.51 (d, J = 14 Hz, together 1H); 4.72 (d, J = 14 Hz); 4.97 (dd, J = 15 and 1 1Hz, together 1H); 7.2-7.6 (m, 4H); 8.0 (s); 8.01 (s, together 1H); 8.26 (s); 8.27 (s, together 1H) ppm.

Example 6

δ = 0.1-1.0 (m, 4H); 2.8-3.5 (m, 2H); 4.1-5.0 (m, 2H); 7.0-7.8 (m, 4H); 8.08 (s); 8.12 (s, together 1H); 8.15 (s); 8.19 (s, together 1H) ppm.

Example 7

δ = 0.1-1.0 (m, 4H); 2.64 (d, J = 5 Hz); 2.79 (d, J = 5 Hz); 2.8 (d, J = 6 Hz); 3.39 (d, J = 6 Hz, together 2H); 4.35 (dd, J = 14 Hz and 1 Hz); 4.54 (d, J = 14 Hz, together 1H); 4.7 (d, J = 14 Hz); 4.7 (dd, J = 14 Hz and 1 Hz, together 1H); 7.3-7.8 (m, 5H); 7.99 (s); 8.01 (s, together 1H); 8.1 (s); 8.22 (s, together 1H) ppm.  

Example 8

δ = 0.1-1.0 (m, 4H); 3.76 (d, J = 5 Hz); 3.0 (d, J = 5 Hz, together 1H); 3.11 (d, J = 5 Hz); 3.3 (d, J = 5 Hz, together 1H); 4.12 (d, J = 15 Hz); 4.52 (d, J = 15 Hz, together 1H); 4.72 (d, J = 15 Hz); 5.0 (d, J = 15 Hz, together 1H); 7.2-7.7 (m, 4H); 8.01 (s, 1H); 8.27 (s, 1H) ppm.

Example 9

δ = 0.1-1.0 (m, 4H); 2.9-3.9 (m, 2H); 4.4-5.2 (m, 2H); 7.2-7.8 (m, 4H); 7.98 (s); 8.0 (s, together 1H); 8.5 (s); 8.52 (s, together 1H) ppm.

Examples of use

In the following examples of use, the compound of the following specified formula used as reference substance:

Known from DE-OS 44 19 812.  

Example A Pyrenophora teres test (barley) / protective

Solvent: 10 parts by weight of N-methyl-pyrrolidone
Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are sprayed with the Active ingredient preparation in the specified application rate.

After the spray coating has dried on, the plants are covered with a Sprayed conidia suspension from Pyrenophora teres. The plants remain 48 Hours at 20 ° C and 100% relative humidity in an incubation cabin.

The plants are grown in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80%.

Evaluation is carried out 7 days after the inoculation.

In this test, the active ingredient (I-1) according to the invention shows in one Application rate of 25 g / ha an efficiency of over 60%, while the Comparative substance (A) has no effect.  

Example B Leptosphaeria nodorum test (wheat) / protective

Solvent: 10 parts by weight of N-methyl-pyrrolidone
Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are sprayed with the Active ingredient preparation in the specified application rate.

After the spray coating has dried on, the plants are covered with a spore sprayed suspension of Leptosphaeria nodorum. The plants remain 48 Hours at 20 ° C and 100% relative humidity in an incubation cabin.

The plants are grown 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.

In this test, the active ingredient (I-1) according to the invention shows one Application rate of 25 g / ha an efficiency of over 70%, while the Comparative substance (A) has no effect.

Claims (7)

1. Oxiranyl triazoles of the formula in which
X represents hydrogen, halogen, alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms,
Z for halogen, alkyl with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms and 1 to 5 halogen atoms, alkoxy with 1 to 4 carbon atoms, haloalkoxy with 1 to 4 carbon atoms and 1 to 5 halogen atoms, nitro or optionally single to triple, similar or phenyl substituted differently by halogen and
m represents the numbers 0, 1, 2 or 3,
as well as their acid addition salts and metal salt complexes. 2. oxiranyl-triazoles of the formula (I) according to claim 1, in which
X represents hydrogen, fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, methoxy and ethoxy,
Z for fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, trichloromethyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, trifluoromethoxy, difluoromethoxy, Nitro or phenyl which is optionally mono- or disubstituted, identical or different, substituted by fluorine and / or chlorine and
m stands for the numbers 0, 1, 2 or 3, where Z can stand for identical or different residues if m stands for 2 or 3. 3. Process for the preparation of oxiranyl triazoles of the formula in which
X represents hydrogen, halogen, alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms,
Z for halogen, alkyl with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms and 1 to 5 halogen atoms, alkoxy with 1 to 4 carbon atoms, haloalkoxy with 1 to 4 carbon atoms and 1 to 5 halogen atoms, nitro or optionally single to triple, similar or phenyl substituted differently by halogen and
m represents the numbers 0, 1, 2 or 3,
as well as their acid addition salts and metal salt complexes, characterized in that hydroxyethyl triazole derivatives of the formula in which
X, Z and m have the meanings given above,
reacted with bases in the presence of a polar diluent and, if appropriate, then adding an acid or a metal salt to the compounds of the formula (I) thus obtained. 4. Microbicidal agents, characterized by a content of at least an oxiranyl triazole of the formula (I) according to claim 1 or on one Acid addition salt or metal salt complex of an oxiranyl triazole Formula (I). 5. Use of oxiranyl-triazoles of the formula (I) according to claim 1 or of their acid addition salts and metal salt complexes as Microbicides in crop protection and material protection. 6. Methods for combating undesirable microorganisms in the Plant protection and material protection, characterized in that one Oxiranyl-triazoles of the formula (I) according to claim 1 or their Acid addition salts or metal salt complexes on the microorganisms and / or their habitat. 7. Process for the preparation of microbicidal agents, thereby characterized in that oxiranyl-triazoles of the formula (I) according to Claim 1 or their metal salt complexes or acid addition salts with Extenders and / or surfactants mixed.