EP1001949A1

EP1001949A1 - Triazoline-thione derivative and its use as a microbicide

Info

Publication number: EP1001949A1
Application number: EP98942628A
Authority: EP
Inventors: Manfred Jautelat; Ralf Tiemann; Stefan Dutzmann; Klaus Stenzel; Gerd Hänssler; Astrid Mauler-Machnik
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1997-08-07
Filing date: 1998-07-25
Publication date: 2000-05-24
Also published as: DE19734185A1; WO1999007686A1; JP2001512719A; AU9069598A

Abstract

The invention relates to a novel triazoline-thione derivative of formula (I), a method for producing said triazoline-thione derivative, and its use as a microbicide for protecting plants and materials.

Description

TRIAZOLINTHION DERIVATIVE AND THEIR USE AS A MICROBICIDE

The present invention relates to a new triazolinethione derivative, a process for its preparation and its use as a microbicide.

It has already become known that numerous mercapto-triazoles or triazolinthione derivatives have fungicidal properties (cf. WO 96-16048). For example, 1,2-dichloro-4,4-dimethyl-5-fluoro-3-hydroxy-3 - [(4,5-dihydro-5-thiono-l, 2,4-triazol-l-yl ) -methyl] -pent-l-en to combat fungi. The effect of this substance is good, but leaves something to be desired in some cases at low application rates.

It now became the new triazolinethione derivative of the formula

found.

Furthermore, it was found that the triazolinethione derivative of the formula (I) can be obtained if 4- (l-chloro-cyclopropyl) -l, l, 2-trichloro-4-hydroxy-5- (l, 2,4- triazol-l-yl) - pent-1-ene of the formula

either

α) reacted successively with lithium diisopropyl amide and sulfur in the presence of a diluent and then hydrolyzed with water, if appropriate in the presence of an acid,

or

β) reacted with sulfur in the presence of a high-boiling diluent and then optionally treated with water and optionally with acid.

Finally, it was found that the new triazolinethione derivative of the formula (I) has very good microbicidal properties and can be used both in crop protection and in material protection to combat unwanted microorganisms, such as fungi.

Surprisingly, the triazolinethione derivative according to the invention shows a better fungicidal activity than the 1,2-dichloro-4,4-dimethyl-5-fluoro-3-hydroxy-3 - [(4,5-dihydro-5-thiono-1,2 , 4-triazol -l-yl) -methyl] -pent-l-en, which is a constitutionally similar, previously known active ingredient with the same direction of action.

The active ingredient according to the invention can be wholly or partly in the "thiono" form of the formula

or in the tautomeric "mercapto" form of the formula

available. For the sake of simplicity, only the "Thiono" shape is listed.

The active ingredient according to the invention contains an asymmetrically substituted carbon atom and can therefore be obtained in optical isomer forms. The present invention relates both to the individual isomers and to their mixtures.

If 4- (l-chloro-cyclopropyl) -l, l, 2-trichloro-4-hydroxy-5- (l, 2,4-triazol-l-yl) - pent-1-ene are placed in succession with lithium diisopropylamide and sulfur powder, the course of the method according to variant (α) can be illustrated by the following formula:

Is 4- (l-chloro-cyclopropyl) -l, l, 2-trichloro-4-hydroxy-5- (l, 2,4-triazol-l-yl) - pent-1-ene with sulfur powder in the presence of N-methyl-pyrrolidone as a diluent, the course of the process according to the invention according to variant (β) can be illustrated by the following formula:

The 4- (1-chloro-cyclopropyl) -1, 1, 2-trichloro-4-hydroxy-5- (1, 2,4-triazol-1 -yl) pent required as starting material for the implementation of the process according to the invention. 1-s of the formula (II) is known (cf. EP-A 0 440 949)

When carrying out the process according to the invention according to variant (α), all inert organic solvents customary for such reactions are suitable as diluents. Ethers, such as tetrahydrofuran, are preferably usable.

Dioxane, diethyl ether and 1,2-dimethoxyethane, furthermore liquid ammonia or also strongly polar solvents, such as dimethyl sulfoxide

Sulfur is preferably used in the form of powder. Hydrolysis is carried out using variant () when carrying out the process according to the invention.

Water, if appropriate in the presence of an acid. All inorganic or organic acids customary for such reactions can be used. Acetic acid, dilute sulfuric acid and dilute hydrochloric acid can preferably be used. However, it is also possible to carry out the hydrolysis using aqueous ammonium chloride solution.

When carrying out the process according to variant (α) according to the invention, the reaction temperatures can be varied within a certain range. In general, temperatures between -70 ° C and + 20 ° C, preferably between -70 ° C and 0 ° C The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to work under increased or reduced pressure.

When carrying out the process according to variant () according to the invention, 1 mol of 4- (1-chloro-cyclopropyl) -1, 1,2-trichloro-4-hydroxy-5- (1,2,4-triazole-1) is used -yl) - pent-1-ene of the formula (II) in general 2 to 3 equivalents, preferably 2.0 to 2.5 equivalents of lithium diisopropylamide and then an equivalent amount or an excess of sulfur. The reaction can be carried out under a protective gas atmosphere, e.g. under nitrogen or argon. The processing takes place according to usual methods. In general, the procedure is such that the reaction mixture is extracted with an organic solvent which is sparingly soluble in water, the combined organic phases are dried and concentrated and the remaining residue is optionally purified by recrystallization and / or chromatography.

When carrying out the process according to variant (β) according to the invention, all high-boiling organic solvents customary for such reactions are suitable as diluents. Amides such as dimethylformamide and dimethylacetamide can preferably be used, furthermore heterocyclic compounds such as N-methyl-pyrrolidone, and also ethers such as diphenyl ether.

Sulfur is also generally used in the form of powder when carrying out the process according to the variant (β). After the reaction, treatment with water and, if appropriate, with acid can optionally be carried out. This is carried out in the same way as the hydrolysis when carrying out the process according to the invention according to variant (α).

The reaction temperatures can be varied within a substantial range when carrying out the process according to variant (β). In general, temperatures between 150 ° C and 300 ° C, preferably between 180 ° C and 250 ° C. When carrying out the process according to the invention according to variant (β), 1 mol of 4- (l-chlorocyclopropyl) -1, 1,2-trichloro-4-hydroxy-5- (1,2,4-triazole- 1-yl) -pent-1-ene of the formula (II) generally 1 to 5 mol, preferably 1.5 to 3 mol, of sulfur. The processing takes place according to usual methods. In general, the procedure is that the reaction mixture is extracted with an organic solvent which is only sparingly soluble in water, the combined organic phases are dried and concentrated, and the remaining residue is freed of any impurities which may be present using customary methods, such as recrystallization or chromatography .

The active ingredient according to the invention has a strong microbicidal action and can be used to combat unwanted microorganisms, such as fungi and bacteria, in crop protection and in material protection.

Fungicides can be used in crop protection to combat Plasmodiophoromyces, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides can be used in plant protection to combat Pseudomonadaceae,

Use RJhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

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, for example, Xanthomonas campestris pv. Oryzae; Pseudomonas species, such as, for example, Pseudomonas syringae pv. Lachrymans; Erwinia species, such as, for example, Erwinia amylovora; Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans; Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis;

Plasmopara species, such as, for example, Plasmopara viticola;

Bremia species, such as, for example, Bremia lactucae;

Peronospora species, such as, for example, Peronospora pisi or P. brassicae; Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca Fülliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea (conidial form: Drechslera, Syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus

(Conidial form: Drechslera, Syn: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita; Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;

Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae; Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens; Alt ernaria species, such as, for example, Alternaria brassicae;

Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.

The fact that the active compound according to the invention is well tolerated by plants in the concentrations required for combating plant diseases permits treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil.

The active ingredient according to the invention can be used with particularly good results in combating diseases in wine, fruit and vegetable growing, for example against real powdery mildew, such as Sphaerotheca, Uncinula, against Erysiphe species and leaf spots, such as Venturia and Alternaria species. Cereal diseases, such as Erysiphe, Leptosphaeria or Pyrenophora species, and rice diseases, such as Pyricularia species, are also combated with good success.

The active ingredient according to the invention is also suitable for increasing the crop yield. It is also less toxic and has good plant tolerance.

In material protection, the substance according to the invention can be used to protect technical ones

Use materials against infestation and destruction by unwanted microorganisms.

In the present context, technical materials are to be understood as non-living materials that have been prepared for use in technology. For example, technical materials which are to be protected from microbial change or destruction by active substances according to the invention can be adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which are attacked or decomposed by microorganisms can be. As part of the to be protected

Materials are also parts of production systems, such as cooling water circuits, that can be affected by the proliferation of microorganisms. In the context of the present invention, technical materials are preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer liquids, particularly preferably wood.

Bacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can break down or change the technical materials. The active compounds according to the invention preferably act against fungi, in particular mold, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae. For example, microorganisms of the following genera may be mentioned:

Alternaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger,

Chaetomium, such as Chaetomium globosum, Coniophora, such as Coniophora puetana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans, Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, like Trichoderma viride,

Escherichia, such as Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa,

Staphylococcus, such as Staphylococcus aureus.

The active ingredient can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV cold and warm mist formulations.

These formulations are made in a known manner, e.g. by mixing the active ingredient with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. In case of using water as

Extenders can, for example, also use organic solvents 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, for example petroleum fractions, alcohols, such as Butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water. With saturated gaseous extenders or carriers are those liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide. The following are suitable as solid carriers: for example, natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates. Possible solid carriers for granules are: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks. Possible emulsifiers and / or foaming agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates. Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes, such as alizarin, azo and metal phthalocyanine dyes and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt,

Molybdenum and zinc can be used.

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

The active ingredient according to the invention, as such or in its formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the spectrum of action or prevent development of resistance. In many cases, synergistic effects are obtained, ie the effectiveness of the mixture is greater than the effectiveness of the individual components.

The following connections can be considered as mixed partners:

Fungicides:

Aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin,

Benalaxyl, benodanil, benomyl, benzamacril, benzamacrylic isobutyl, bialaphos, binapacrylic, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,

Calcium polysulfide, capsimycin, captafol, captan, carbendazim, carboxin, carvon,

Quinomethionate (quinomethionate), chlobenthiazon, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,

Debacarb, dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazol-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dorphianolodin, dithianonodonone,

Ediphenphos, Epoxiconazole, Etaconazole, Ethirimol, Etridiazole,

Famoxadone, fenapanil, fenarimol, fenbuconazole, fenfüram, fenitropan, fenpiclonil, fenpropidine, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzon, fluazinam, flumetover, fluoromid, fluquinconazole, flurprimolol, flusulfanolidol, flusulfanolidol, flusulfanolidol, flusulfanolidol, flusulfanolidol, flusulfazolidol, flusulfanolidol, flusulfanolidol, flusulfanolidol, flusulfanolidol, flusulfanilidol, flusulfanolidol, flusulfanolidol, flusulfanolidol, flusulfanolidol, flusulazololid Alminium, fosetyl sodium, fthalide,

Fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis, furmecyclox, Guazatin,

Hexachlorobenzene, hexaconazole, hymexazole,

Imazalil, Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Irumamycin, Isoprothiolan, Isovaledione,

Kasugamycin, Kresoxim-methyl, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxy-copper and

B ordeaux mix,

Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfüroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,

Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,

Ofurace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,

Paclobutrazol, Pefürazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin, Polyoxorim, probenazole, Prochloraz, Procymidon, Propamocarb, Propanosine-Sodium, Propiconazole, Propineb, Pyrazophos, Pyrifen, Pyifen, Pyroyilonil

Quinconazole, quintozen (PCNB),

Sulfur and sulfur preparations,

Tebuconazole, tecloftalam, tecnazen, tetcyclacis, tetraconazole, thiabendazole,

Thicyofen, Thifluzamide, Thiophanate-methyl, Thiram, Tioxymid, Tolclofos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazbutil, Triazoxid, Trichlamid, Tricyclazol, Tridemorph, Triflumizol, Triforin, Triticonazole, Uniconazole,

Validamycin A, vinclozolin, viniconazole, zarilamide, zineb, ziram and Dagger G,

OK-8705, OK-8801, α- (1, 1-dimethylethyl) -ß- (2-phenoxyethyl) - 1 H-1, 2,4-triazole-1-ethanol, α- (2,4-dichlorophenyl) -ß-fluoro-b-propyl- 1 H- 1, 2,4-triazole-1-ethanol, - (2,4-dichlorophenyl) -ß-methoxy-a-methyl- 1 H- 1, 2,4- triazol-1-ethanol, α- (5-methyl-l, 3-dioxan-5-yl) -ß - [[4- (trifluoromethyl) -phenyl] -methylene] -lH-l, 2,4-triazole- 1-ethanol,

(5RS, 6RS) -6-hydroxy-2,2,7,7-tetramethyl-5- (1H-l, 2,4-triazol-l-yl) -3-octanone, (E) -a- (methoxyimino ) -N-methyl-2-phenoxy-phenylacetamide, {2-methyl-l - [[[[l- (4-methylphenyl) ethyl] amino] carbonyl] propyl} carbamic acid-

1-isopropyl ester l- (2,4-dichlorophenyl) -2- (lH-l, 2,4-triazol-l-yl) -ethanone-O- (phenylmethyl) oxime,

1 - (2-methyl-1-naphthalenyl) - 1 H-pyrrole-2, 5-dione,

1 - (3, 5-dichlorophenyl) -3 - (2-propenyl) -2, 5-pyrrolidinedione, 1 - [(diiodomethyl) sulfonyl] -4-methyl-benzene, l - [[2- (2.4 -Dichlorophenyl) -l, 3-dioxolan-2-yl] methyl] -lH-imidazole, l - [[2- (4-chlorophenyl) -3-phenyloxiranyl] methyl] -lH-l, 2,4- triazole, l- [l- [2 - [(2,4-dichlorophenyl) methoxy] phenyl] ethenyl] -lH-imidazole, l-methyl-5-nonyl-2- (phenylmethyl) -3-pyrrolidinol, 2 ', 6 ^, -dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-l, 3-thiazole-5-carboxanilide,

2,2-dichloro-N- [1- (4-chlorophenyl) ethyl] -l-ethyl-3-methyl-cyclopropanecarboxamide,

2,6-dichloro-5- (methylthio) -4-pyrimidinyl-thiocyanate,

2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide, 2,6-dichloro-N - [[4- (trifluoromethyl) phenyl] methyl] benzamide,

2- (2,3,3-triiodo-2-propenyl) -2H-tetrazole,

2 - [(l-methylethyl) sulfonyl] -5- (trichloromethyl) -1, 3,4-thiadiazole, 2 - [[6-Deoxy-4-O- (4-O-methyl-β-D-glycopyranosyl) -aD-glucopyranosyl] amino] -4- methoxy-lH-pyrrolo [2,3-d] pyrimidine- 5-carbonitrile,

2-aminobutane,

2-bromo-2- (bromomethyl) pentandinitrile, 2-chloro-N- (2,3-dihydro-1,3,1-trimethyl-1 H-inden-4-yl) -3-pyridinecarboxamide,

2-chloro-N- (2,6-dimethylphenyl) -N- (isothiocyanatomethyl) acetamide,

2-phenylphenol (OPP),

3,4-dichloro-l- [4- (difluoromethoxy) phenyl] -IH-pyrrole-2,5-dione,

3,5-dichloro-N- [cyan [(1-methyl-2-propynyl) -oxy] -methyl] -benzamide, 3 - (1, 1-dimethylpropyl-1-oxo-1 H-indene-2-carbonitrile ,

3- [2- (4-chlorophenyl) -5-ethoxy-3-isoxazolidinyl] pyridine,

4-chloro-2-cyan-N, N-dimethyl-5- (4-methylphenyl) -lH-imidazole-l-sulfonamide,

4-methyl-tetrazolo [1,5-a] quinazolin-5 (4H) -one,

8- (l, l-dimethylethyl) -N-ethyl-N-propyl-l, 4-dioxaspiro [4.5] decane-2-methanamine, 8-hydroxyquinoline sulfate,

9H-xanthene-9-carboxylic acid 2 - [(phenylamino) carbonyl] hydrazide, bis- (l-methylethyl) -3-methyl-4 - [(3-methylbenzoyl) -oxy] -2,5-thiophene dicarboxylate, ice-1 - (4-chlorophenyl) -2- (1 H-1, 2,4-triazole-1-yl) cycloheptanol, cis-4- [3- [4- (l, l-dimethylpropyl) phenyl -2-methylpropyl] -2,6-dimethyl-morpholine hydrochloride,

Ethyl - [(4-chlorophenyl) azo] cyanoacetate,

Potassium hydrogen carbonate,

Methane tetrathiol sodium salt,

Methyl 1 - (2,3-dihydro-2,2-dimethyl-1 H-inden-1-yl) - 1H-imidazole-5-carboxylate, methyl N- (2,6-dimethylphenyl) -N- ( 5-isoxazolylcarbonyl) -DL-alaninate,

Methyl N- (chloroacetyl) -N- (2,6-dimethylphenyl) -DL-alaninate,

N- (2,3-dichloro-4-hydroxyphenyl) -l-methyl-cyclohexane carboxamide.

N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-furanyl) acetamide,

N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-thienyl) acetamide, N- (2-chloro-4-nitrophenyl) -4-methyl-3-nitro- benzenesulfonamide,

N- (4-Cyclohexylphenyl) -l, 4,5,6-tetrahydro-2-pyrimidinamine, N- (4-hexylphenyl) - 1,4,5, 6-tetrahydro-2-pyrimidinamine, N- (5-chloro -2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) acetamide, N- (6-methoxy) -3-pyridinyl) cyclopropanecarboxamide,

N- [2, 2, 2-trichloro-1 - [(chloroacetyl) amino] ethylj-benzamide,

N- [3-chloro-4,5-bis (2-propynyloxy) phenyl] -N'-methoxymanimidamide,

N-formyl-N-hydroxy-DL-alanine sodium salt,

O, O-diethyl- [2- (dipropylamino) -2-oxoethyl] ethylphosphoramidothioate,

O-methyl-S-phenyl-phenylpropylphosphoramidothioate,

S-methyl-l, 2,3-benzothiadiazole-7-carbothioate, spiro [2H] -l-benzopyran-2, r (3Η) -isobenzofüran] -3'-one,

Bactericides:

Bromopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, teclofalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides:

Abamectin, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, 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, benufracarb, bensultap, betacyfluthrin, bifenthrin, BPMC , Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxim, Butylpyridaben,

Cadusafos, Carbaryl, Carbofüran, Carbophenothion, Carbosulfan, Cartap, Chloetho- carb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos, N - [(6-Chloro-3-pyridinyl) -methyl] -N'-cyano-N-methyl -ethanimidamides, chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezin, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine, Deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflubenzuron, dimethoate,

Dimethylvinphos, dioxathione, disulfoton,

Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos, Etrimphos,

Fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb,

Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronii, Fluazinam, Fluazuron, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenprox, Fluvalinate, Fonophos, Formothion, Fosthiazat, Fubfenarbx, Furathi

HCH, heptenophos, hexaflumuron, hexythiazox,

Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,

Lambda cyhalothrin, lufenuron,

Malathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,

Naled, NC 184, Nitenpyram

Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,

Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenophos, Prome- carb, Propaphos, Propoxur, Prothiophos, Prothoat, Pymetophosin, Pyridlentin Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen, Quinalphos,

Salithion, Sebufos, Srlafluofen, Sulfotep, Sulprofos,

Tebufenozide, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos,

Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomethrin, Triarathen, Triazophos, Triazuron, Trichlorofon, Triflumuron, Trimethacarb,

Vamidothione, XMC, xylylcarb, zetamethrin.

A mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators, is also possible.

The active ingredient can be used as such, in the form of its formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by pouring, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredient by the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of the plants can also be treated.

When using the active ingredient according to the invention as a fungicide, the application rates can be varied within a substantial range, depending on the type of application.

In the treatment of parts of plants, the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha. In the case of seed treatment, the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. When treating the soil, they are

Application rates of active ingredient generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha. The agents used to protect industrial materials generally contain the active ingredient in an amount of 1 to 95% by weight, preferably 10 to 75% by weight.

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

The effectiveness and the spectrum of activity of the active ingredient to be used according to the invention in the protection of materials, or of the agents, concentrates or very generally formulations which can be prepared therefrom, can be increased if further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or other active ingredients are used to increase the spectrum of activity or Achieving special effects such as added protection against insects. These mixtures can have a broader spectrum of activity than the active ingredient according to the invention.

The preparation and use of the active ingredient according to the invention is illustrated by the following examples.

Manufacturing example

In a mixture of 6.58 g (20 mmol) of 4- (l-chloro-cyclopropyl) -l, l, 2-trichloro-4-hydroxy-5- (l, 2,4-triazol-l-yi) - Pent-1-ene in 50 ml of absolute tetrahydrofuran is added dropwise at -70 ° C. with stirring, 20 ml (40 mmol) of a 2-molar solution of lithium diisopropyl amide in tetrahydrofuran. After the addition has ended, the mixture is stirred for a further hour at -70 ° C. and then mixed with 1.28 g (40 mmol) of sulfur powder. The reaction mixture is then at -70 ° C for one hour and then

Stirred at 0 ° C for 2 hours. The reaction mixture is then diluted with ethyl acetate and shaken out several times with saturated, aqueous ammonium chloride solution.

The organic phase is dried over sodium sulfate and then concentrated under reduced pressure. The resulting crude product is recrystallized twice from 5 ml of toluene. In this way 4- (l-chloro-cyclopropyl) -l, 1,2-trichloro-4-hydroxy-5- (4,5-dihydro-5-thiono-l, 2,4-triazole-l- yl) -pent-l-en in the form of a solid with a melting point of 129-130 ° C.

ⁱ H-NMR spectrum (400 MHz, CDC1 ₃ , TMS): δ = 0.8-1.3 (m, 4H); 3.2 (d. 1H); 3.3 (d. 1H); 4.55 (OH); 4.75 (AB, 2H); 7.9 (s, 1H); 12.3 (NH) Examples of use

Example A

Sphaerotheca test (cucumber) / protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight is mixed

Active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Sphaerotheca Fülliginea. The plants are then placed in the greenhouse at about 23 ° C. and a relative atmospheric humidity of about 70%.

Evaluation is carried out 10 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

Active substances, application rates and test results are shown in the following table.

Table A

Sphaerotheca test (cucumber) / protective

Active ingredient application rate Efficacy of active ingredient in% in g / ha

Known from WO 96-16048:

(A) 10 43

According to the invention

(I) 10 93

Example B

Venturia test (apple) / protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of alkylaryl polyglycol ether

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.

To test for protective activity, young plants are sprayed with the active compound preparation in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the Venturia inaequalis apple scab pathogen and then remain in an incubation cabin at about 20 ° C. and 100% relative atmospheric humidity for 1 day.

The plants are then placed in the greenhouse at approx. 21 ° C. and a relative humidity of approx. 90%.

Active substances, application rates and test results are shown in the following table. Table B

Venturia test (apple) / protective

Example C

Pyrenophora teres test (barley) / curative

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

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 mixture is diluted

Concentrate with water to the desired concentration.

To test for curative effectiveness, young plants are sprayed with a conidia suspension of Pyrenophora teres. The plants remain in an incubation cabin at 20 ° C. and 100% relative atmospheric humidity for 48 hours. Then the

Plants sprayed with the active ingredient preparation in the application rate indicated.

The plants are placed 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. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

Active substances, application rates and test results are shown in the following table. Table C.

Pyrenophora teres test (barley) / curative

Example D

Erysiphe test (wheat) / protective

Concentrate with water to the desired concentration.

To test for protective activity, young plants are sprayed with the active compound preparation in the stated application rate.

After the spray coating has dried on, the plants are spotted with Erysiphe graminis fisp. tritici pollinated.

The plants are placed in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80% in order to promote the development of mildew pustules.

Erysiphe test (wheat) / protective

Active ingredient application rate Efficacy of active ingredient in% in g / ha

Known from WO 96-16048:

(A) 250 88

According to the invention

(I) 250 100

Claims

claims

1. Triazolinthione derivative of the formula

2. Process for the preparation of the triazolinethione derivative of the formula (I) according to

Claim 1, characterized in that 4- (l-chloro-cyclopropyl) - 1, 1,2-trichloro-4-hydroxy-5- (l, 2,4-triazol-l-yl) -pent-l- of the formula

either

or

ß) with sulfur in the presence of a high-boiling diluent and then optionally treated with water and optionally with acid.

3. Microbicidal agents, characterized by a content of triazolinethione derivative of the formula (I) according to claim 1 in addition to extenders and / or surface-active substances.

4. Use of triazolinthione derivative of the formula (I) according to claim 1 as a microbicide.

5. A method of combating undesirable microorganisms, characterized in that triazolinethione derivative of the formula (I) according to claim 1 is applied to the microorganisms and / or their habitat.

6. A process for the preparation of microbicidal agents, characterized in that triazolinethione derivative of the formula (I) according to Claim 1 is mixed with extenders and / or surface-active substances.