EP0915885A1 - Pyrazine derivatives and their use for material and plant protection - Google Patents

Abstract

New and partially known pyrazine derivatives have the formula (I), in which R<1>, R<2> and A have the meanings given in the description. Also disclosed are a process for preparing the same and their use for protecting technical materials from microbial infestation.

Description

 PYRAZINE DERIVATIVES AND THEIR USE IN MATERIAL AND PLANT PROTECTION

The invention relates to new and partially known pyrazine derivatives, processes for their preparation and their use in material and crop protection

It has already become known that 1,3-dithiolo- and 1,4-dithioquinooxalines have an antifungal and an antifouling effect (see WO 93/13106; US Pat. No. 3,761,475). However, these compounds have an intense yellow to orange color, which is why they are not suitable for protecting colorless, white or light technical materials, such as emulsion paints

2- (1,3-dithia-4,7-diaza-indan-2-ylidenes) -malononitrile is also known. For this compound, an activity as an antifouling agent, as a malaπa agent and as a protection against radiation has been described (see US Pat. No. 4 168 174, Foye, WO et al, J Pharm Sei 64, 21 1 (1975), Foye, WO, J Pharm. Sei 57, 161 1 (1968))

Surprisingly, it has now been found that compounds of the general

Formula (I)

in which

R ¹ and R ² independently of one another represent hydrogen, halogen, alkyl or haloalkyl and

A stands for.

in which

R ³ and R ^{4 are} -NO ₂ , -CN, -SO ₂ R ⁵ , -COOR ⁵ , -COR ⁵ and -CONR ⁵ R ⁶ , where R ⁵ and R ^{6 represent} hydrogen, alkyl or aryl,

are also very suitable as microbicides for protecting technical materials and plants. They are also colorless or only very weakly colored, which makes them particularly suitable for use as material protection agents

Formula (I) provides a general definition of the pyrazine derivatives used according to the invention. Compounds of the general formula (I) are preferred

in which

R ¹ and R ² independently of one another represent hydrogen, halogen, branched or linear alkyl having 1 to 8 carbon atoms or haloalkyl having 1 to 6 carbon atoms and 1 to 9 identical or different halogen atoms and

stands.

in which

R ³ and R ^{4 are} -NO ₂ , -CN, -SO, R ⁵ , -COOR ⁵ , -COR ⁵ and -CONR ⁵ R ⁶ , where

R ⁵ and R ^{6 represent} hydrogen, branched or linear alkyl having 1 to 8 carbon atoms or optionally substituted aryl

Compounds of the general formula (I) in which

R ¹ and R ² independently of one another represent hydrogen, chlorine, bromine, fluorine, branched or linear alkyl having 1 to 6 carbon atoms or haloalkyl having 1 to 4 carbon atoms and 1 to 7 fluorine and / or chlorine atoms

R ¹ and R ² are in particular hydrogen and chlorine A stands for • * ■ or stands for

in which

R ³ and optionally R ^{4 are} -NO ₂ , -CN, -S0 ₂ R ⁵ , -COOR ⁵ , -COR ⁵ and -CONR ⁵ R ⁶ , in which

R ⁵ and optionally R ⁶ for hydrogen, branched or linear

Alkyl with 1 to 6 carbon atoms such as methyl, ethyl, n-, i-propyl, n-, i-, t-, s-butyl or optionally 1 to 3 times with halogen, alkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio , Acyl, acyloxy, CN, NO ₂ substituted phenyl

R ³ stands in particular for CN or COO alkyl.

R ⁴ stands in particular for CN, SO ₂ alkyl, SO ₂ phenyl, COO alkyl or CONH alkyl.

Alkyl in the present application, insofar as the radical is mentioned individually or as a compound, such as in haloalkyl or alkoxy, especially for

Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl phenyl is optionally and preferably substituted by alkyl.

The compounds of the general formula (I) are new, except for the representative in whom

R ¹ = R ² = H,

R> 3 ^J = _ R _D 4 ⁴ = CN (see also US-PA 4 168 174) The known and new pyrazine pivates of the general formula (I) are obtained, in which

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and A have the meaning given above,

if pyrazine derivatives of the general formula (II)

in which

R ¹ and R ^{2 have} the meaning given above and

Shark represents halogen, preferably chlorine or bromine,

optionally in the presence of diluents and acid binders with salts of the formula (III)

M ^{+ "} S

\

A (HI),

/

IVf S

in which

A, R ⁴ , R ⁵ and R ^{6 have} the meaning given above and M * represents a mono- or polyvalent cation, preferably K ⁺ , Na ⁺ and NH ₄ ⁺

The reaction temperatures can be varied within a wide temperature range in this process. In general, the process is carried out between 0 ° C. and 250 ° C., preferably between + 20 ° C. and + 150 ° C. The reactions are optionally carried out in the presence of acid binders, all of which are customary Acid-binding agents are used. These preferably include tertiary amines such as methylamine and pyridine, alkali metal hydroxides such as sodium and potassium hydroxide and alkali carbonates and hydrogen carbon such as potassium carbonate and sodium hydrogen carbonate.

All inert organic solvents are suitable as diluents which may be used. These preferably include hydrocarbons such as toluene, xylene or hexane; chlorinated hydrocarbons such as chlorobenzene and

Chloroform; Ketones such as acetone; Ethers such as tetrahydrofuran, diethyl ether, methyl tert-butyl ether and dioxane; Nitriles such as acetonitrile, amides such as dimethylformamide and dimethylacetamide, and dimethyl sulfoxide.

The pyrazine derivatives of the formula (II) are known or can be prepared by known processes (see, for example, J. Adachi et al., J. Org. Chem. 37, 221 (1972);

Yudin, I.L. Mendeleev Commun. 196 (1995); GB 1 342 598).

The salts of the general formula (III) are also known or can be prepared by known processes (see, for example, WO Foye et al., J. Pharm. Sei, 64, 21 1 (1975); R. Go pper et al., Chem Ber. 99, 2885 (1966), U.S. Patent 4,970,228; KA Jensen et al., Acta Chem. Scand. 22, 1,107 (1968)).

The active compounds of the formula (I) have a strong microbicidal action and can be used practically to combat unwanted microorganisms. The active compounds of the formula (I) are suitable for protecting industrial materials against attack and destruction by undesired microorganisms.

In the present context, technical materials are understood to mean non-living materials that have been prepared for use in technology. For example, technical materials that are to be protected against microbial change or destruction by active substances according to the invention, adhesives, glues, paper and cardboard, textiles, leather, wood,

Paint and plastic items, cooling lubricants and other materials that can be attacked or decomposed by microorganisms. In the context of the materials to be protected, parts of production plants, for example cooling water circuits, may also be mentioned which can be impaired by the multiplication of microorganisms. In the context of the present invention, adhesives, glues, papers and Cardboard boxes, leather, wood, paints, cooling lubricants and cooling circuits

Bacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can cause degradation or a change in the technical materials. The ones according to the invention preferably act

Active substances against fungi, in particular mold, wood-staining and wood-destroying fungi (Basidiomycetes), as well as 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, like Chaetomium globosum,

Coniophora, such as Coniophora puteana,

Lentinus, such as Lentinus tigrinus,

Peniciliium, 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

Depending on their respective physical and / or chemical properties, the active compounds of the formula (I) can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and very fine encapsulations in polymeric substances

These formulations or agents are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foams Generating agents If water is used as an extender, organic solvents can also be used as auxiliary solvents, for example. Aromatics such as xylene, toluene, alkylnaphthalenes and chlorinated solvents are essentially suitable 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 or dimethyl sulfoxide, and water; Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; Solid carrier materials are suitable: for example natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates; Solid carriers for granules are possible: for example broken and fractionated natural rocks such as caicit, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well

Granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foam-generating agents are possible. e.g. non-ionic 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, as dispersants are possible: e.g. Lignin sulfite liquor and methyl cellulose.

Adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-shaped polymers, 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 effectiveness and the spectrum of activity of the active compounds of the formula (I) or the agents, precursors or very generally formulations which can be prepared therefrom can be increased if further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or other active compounds are optionally used to enlarge the spectrum of activity or to achieve special effects such as additional protection against insects. These mixtures can have a broader spectrum of activity than the compounds according to the invention.

In many cases, synergistic effects are obtained, i.e. the effectiveness of

Mixing is greater than the effectiveness of the individual components. Particularly favorable mix partners are e.g. the following connections:

Triazoles such as:

Amitrole, Azocyclotin, BAS 480F, Bitertanol, Difenoconazole, Fenbuconazole, Fenchlorazole, Fenethanil, Fluquinconazole, Flusilazole, Flutriafol, Imibenconazole, Isozofos, Myclobutanil, Metconazole, Epoxyconazole, Paclobutonol, 1-pentoconobonazole, 1 - (4-chlorophenyl) -2- (1 H- 1, 2,4-triazol-1-yl) -cycloheptanol, tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole, triticonazole, uniconazole and their metal salts and acid adducts .

Imidazoles such as: lmazalil, pefurazoate, prochloraz, triflumizole, 2- (l-tert-butyl) -l- (2-chlorophenyl) -3- (l, 2,4-triazol-l-yl) -propan-2-ol , Thiazole carboxanilides such as 2 ', 6'-dibromo-2-methyl-4-trifluoromethoxy-4'-trifluoromethyl-l, 3-thiazole-5-carboxanilide, 1-imidazol-yl-l- (4'-chlorophenoxy) -3,3-dimethylbutan-2-one and their metal salts and acid adducts.

Methyl (E) -2- [2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylates, methyl (E) -2- [2- [6 (2-thioamidophenoxy) pyrimidine- 4-yloxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [6- (2-fluorophenoxypyrimidin-4-yloxy] phenyI] -3-methoxyacrylate, methyl (E) -2- [ 2- [6- (2,6-difluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate,

Methyl (E) -2- [2- [3- (pyrimidin-2-yloxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (5-methylpyrimidin-2-yloxy ) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (phenylsulfonyloxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- [4-nitrophenoxy] phenoxy] phenyl] 3-methoxyacrylates,

Methyl (E) -2- [2-phenoxyphenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3,5-dimethylbenzoyl) pyrrol-l-yl] -3-methoxyacrylate, methyl (E) - 2- [2- [3-methoxyphenoxy) phenyl] -3-methoxyacrylates, Methyl (E) -2- [2- [2-phenylethen-1-yl) phenyl] -3-methoxyacrylate,

Methyl (E) -2- (2 [3,5-dichlorophenoxy] pyridin-3-yI) -3-methoxyacrylates,

Methyl (E) -2- (2- (3- (1,1,2,2-etrafluoroethoxy) phenoxy) phenyl) -3-methoxyacrylate,

Methyl (E) -2- (2- [3- (α-hydroxybenzyl) phenoxy] phenyl) -3-methoxyacrylate,

Methyl (E) -2- (2 (4-phenoxypyridin-l-yloxy) phenyl) -3-methoxyacrylate,

Methyl (E) -2- [2- (3-n-propy 1 oxyphenoxy) phenyl] -3 -m ethoxy acrylic late,

Methyl (E) -2- [2- (3-isopropyloxyphenoxy) phenyl] -3-methoxyacrylate,

Methyl (E) -2- [2 [3- (2-fluorophenoxy) phenoxy] phenyl] -3-methoxyacrylates,

Methyl (E) -2- [2- (<3-ethoxyphenoxy) phenyl] -3-methoxyacrylate,

Methyl (E) -2- [2 (4-tert-butylpyridin-2-yloxy) phenyl] -3-methoxyacrylate,

Methyl (E) -2- [2- [3- (3-cyanophenoxy) phenoxy] phenyl] -3-methoxyacrylate,

Methyl (E) -2- [2 (3-methylpyridin-2-yloxymethyl) phenyl] -3-methoxyacrylate,

Methyl (E) -2- [2- [6 (2-methylphenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate,

Methyl (E) -2- [2- (5-bromopyridin-2-yloxymethyl) phenyl] -3-methoxyacrylate,

Methyl (E) -2- [2- (3- (3-iodopyridin-2-yloxy) phenoxy) phenyl] -3-methoxyacrylates,

Methyl (E) -2- [2- [6- (2-chloropyridin-3-yloxy) pyrimidin-4-yloxy] phenyl] -3-methoxy-acrylates,

(E), (E) -methyl-2- [2- (5,6-dimethylpyrazin-2-ylmethyloximinomethyl) phenyl] -3-methoxyacrylates,

(E) -methyl-2- (2- [6- (6-methylpyridin-2-yloxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylates,

(E), (E) -methyl-2- {2- (3-methoxyphenyl) methyloximinomethyl] phenyl} -3-methoxy-acrylates,

(E) -methyl-2- {2- [6- (2-azidophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxy-acrylates,

(E), (E) -methyl-2- {2- [6-phenylpyrimidin-4-yl) methyloximinomethyl] phenyl} -3-methoxyacrylates,

(E), (E) -methyl-2- {2 - [(4-chlorophenyl) methyloximinomethyl] phenyl} -3-methoxy-acrylates,

(E) -methyl-2- {2- [6- (2-n-propylphenoxy) -1, 3,5-triazin-4-yloxy] phenyl} -3-methoxy-acrylates,

(E), (E) -methyl-2- {2 - [(3-nitrophenyl) methyloximinomethyl] phenyl} -3-methoxyacrylate. Succinate dehydrogenase inhibitors such as:

Fenfuram, Furcarbanil, Cyclafluramid, Furmecyclox, Seedvax, Metsulfovax, Pyrocarbolide, Oxycarboxin, Shirlan, Mebenil (Mepronil), Benodanil, Flutolanil

(Moncut) naphthalene derivatives such as:

Terbinafine, naftifine, butenafine, 3-chloro-7- (2-aza-2,7,7-trimethyl-oct-3-en-5-in)

Sulfenamides such as dichlorfluanide, tolylfluanid, folpet, fluorfolpet; Captan,

Captofol,

Benzimidazoles such as carbendazim, benomyl, furathiocarb, fuberidazole, thiophonate methyl, thiabendazole or their salts;

Morpholine derivatives such as tridemoprh, fenpropimorph, falimorph, dimethomorph,

Dodemorph, aldimorph, fenpropidine and their arylsulfonic acid salts, such as p-

Toluenesulfonic acid and p-dodecylphenyl sulfonic acid;

Dithiocarbamate, Cufraneb, Ferbam, Mancopper, Mancozeb, Maneb, Metam, Metiram, Thiram Zeneb, Ziram;

Benzothiazoles such as 2-mercaptobenzothiazole,

Benzothiophene dioxides, such as benzothiophene-2-carboxylic acid cyclohexylamine dioxide,

Benzamides such as 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamides,

Boron compounds such as boric acid, boric acid ester, borax; Formaldehyde and formaldehyde releasing compounds such as benzyl alcohol mono-

(poly) hemiformal, oxazolidine, hexa-hydro-S-triazine, N-methylolchloroacetamide,

Paraformadehyde, nitropyrin, oxolinic acid, tecloftalam;

Tris-N- (cyclohexyldiazeniumdioxy) aluminum, N- (cyclohexyldiazeniumdioxy) - tributyltin or K salts, bis-N- (cyclohexyldiazeniumdioxy) copper N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin- 3-one, 4,5-dichloro-N-oc-tylisothiazolin-3-one, N-octyl-isothiazolin-3-one, 4,5-trimethylene-isothiazolinone,

4,5-benzisothiazolinone, N-methylolchloroacetamide;

Aldehydes such as cinnamaldehyde, formaldehyde, glutardialdehyde, β-bromocinnamaldehyde,

Thiocyanates such as thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate, etc., quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride,

Benzyldimethyldodecylammonium chloride, didecyldimethaylammonium chloride;

Iodine derivatives such as diiodomethyl-p-tolylsulfone, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodoproparformal, 3-bromo-2,3-diiodo-2-propenylethyl carbamate, 2,3,3-triiodo allyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl-n-butyl carbamate, 3-iodo-2-propynyl-n-hexyl carbamate, 3-iodo-2-propynyl cyclohexyl carbamate, 3-

Iodine-2-propynylphenyl carbamate; Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol,

3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophen, o-phenylphenol, m-

Phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol and their alkali and

Alkaline earth metal salts. Microbicides with activated halogen group such as chloroacetamide, bronopol, bronidox, tectamer such as 2-bromo-2-nitro-l, 3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 2,2-dibromo-3- nitrile propionamide, 1,2-dibromo-2,4-dicyanobutane, β-bromo-β-nitrostyrene;

Pyridines such as l-hydroxy-2-pyridinthione (and their Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine, pyrimethanol, mepanipyrim, dipyrithione, 1-

Hydroxy-4-methyl-6- (2,4,4-trimethylpentyl) -2 (1H) pyridine;

Metal soaps such as tin, copper, zinc naphtenate, octoate, 2-ethylhexanoate, oleate,

-phosphate, -benzoate;

Metal salts such as copper hydroxycarbonate, sodium dichromate, potassium dichromate, potassium chromate, copper sulfate, copper chloride, copper borate, zinc fluorosilicate,

Copper fluorosilicate.

Oxides such as tributyltin oxide, Cu ₂ O, CuO, ZnO;

Dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates,

Tetramethylthiuram disulfide, potassium N-methyldithiocarbamate; Nitriles such as 2,4,5, 6-tetrachloroisophthalonitrile, disodium cyano-dithioimidocarbamate;

Quinolines such as 8-hydroxyquinoline and their Cu salts;

Mucochloric acid, 5-hydroxy-2 (5H) furanone;

4,5-dichlorodithiazolinone, 4,5-benzdithiazolinone, 4,5-trimethylene dithiazolinone, 4,5-dichloro- (3H) -l, 2-dithiol-3-one, 3,5-dimethyl-tetrahydro-l, 3, 5-thiadiazin-2-thione,

N- (2-p-chlorobenzoylethyl) hexaminium chloride, potassium N-hydroxymethyl-N'-methyl-dithiocarbamate,

2-oxo-2- (4-hydroxy-phenyl) acethydroximic acid chloride,

Phenyl- (2-chloro-cyanovinyl) sulfone, phenyl- (1,2-dichloro-2-cyanovinyl) sulfone;

Zeolites containing Ag, Zn or Cu alone or included in polymers

Active ingredients.

Mixtures with are very particularly preferred

Azaconazole, bromuconazole, cyproconazole, dichlobutrazole, diniconazole, hexaconazole, metaconazole, penconazole, propiconazole, tebuconazole, methyl -

(E) -methoximino [α- (o-tolyloxy) -o-tolyl)] acetate, methyl- (E) -2- {2- [6- (2-cyanophen- oxy) pyrimidin-4-yl-oxy] phenyl} -3-methoxyacrylate, methfuroxam, carboxin, fen- piclonil, 4- (2,2-difluoro-l, 3-benzodioxol-4-yl) -lH-pyrrole- 3-carbonitrile, butenafine, imazalil, N-methyl-isothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, N-octylisothiazolin-3-one, benzisothiazolinone, N- (2-hydroxypropyl) -amino- methanol, benzyl alcohol (hemi) formal, glutaraldehyde, omadine, dimethyl dicarbonate, and / or 3-iodo-2-propynyl-n-butyl carbamate.

Furthermore, well-effective mixtures with the following active ingredients are also produced:

Fungicides: Acypetacs, 2-aminobutanes, ampropylfos, anilazines, benalaxyl, bupirimate,

Quinomethionate, Chloroneb, Chlozolinate, Cymoxanil, Dazomet, Diclomezine, Dichloram, Diethofencarb, Dimethirimol, Diocab, Dithianon, Dodine, Drazoxolon, Edifenphos, Ethirimol, Etridiazole, Fenarimol, Fenitropan, Flomidulamone, Hydroxidomamidone, Fentinamide, Fentin acetate, Flutriafol, Fosetyl, Fthalide, Furalaxyl, Guazatine, Hymexazol, Iprobefos, Iprodione, Isoprothiolane,

Metalaxyl, methasulfocarb, nitrothal-isopropyl, Nuarimol, Ofurace, Oxadiyl, Perfluorazoate, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Procymidone, Prop-amocarb, Propineb, Pyrazophos, Pyrifenox, Pyroquilon, Quintozene, Quintozene, Quintozene , Thiophanate-methyl, Tolclofos-methyl, Triazoxide, Trichlamide, Tricyclazole, Triforine, Vinclozolin.

Insecticides:

Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, α-l (4-chlorophenyl) -4- (O-ethyl, S-propyl) phosphoryloxy-pyrazole, chlorpyrifos, Coumaphos, Demeton, Demeton-S-methyl, diazinon, dichlorvos, Dimethoate, Ethoate, Ethoprophos, Etrimfos, Fenitrothion, Fenthion, Heptenophas, Parathion, Parathion-methyl,

Phosalones, phoxim, pirimiphos-ethyl, pirimiphos-methyl, profenofos, prothiofos, sulfprofos, triazophos and trichlorphone;

Carbamates such as aldicarb, bendiocarb, α-2- (l-methylpropyl) phenylmethyl carbamate, butocarboxime, butoxycarboxime, carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methoyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarb;

Organosilicon compounds, preferably dimethyl (phenyl) silyl-methyl-3-phenoxybenzyl ether such as dimethyl- (4-ethoxyphenyl) -silylmethyl-3-phenoxybenzylether or (Dimethylphenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether such as dimethyl- (9-ethoxyphenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether or [(phenyl) -3- (3-phenoxyphenyl) - propyl] (dimethyl) silanes such as (4-ethoxyphenyl) - [3- (4-fluoro-3-phenoxyphenylpropyl] dimethyl silane, silafluofen; pyrethroids such as allethrin, alphamethrin, bioresmethrin, byfenthrin, cycloprothrin,

Cyfluthrin, decamethrin, cyhalothrin, cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- (2-chloro-2-trifluoromethylvinyl) cyclopropane carboxylate, fenpropathrin, fenfluthrin, fenvalerate , Flucythrinate, flumethrin, fluvalinate, permethrin, resmethrin and tralomethrin; Nitroimines and nitromethylenes such as l - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-

N-nitro-1H-imidazole-2-amine (imidacloprid), N - [(6-chloro-3-pyridyl) methyl-] N ² - cyano-N'-methylacetamide (NI-25);

Abamectin, AC 303, 630, Acephate, Acrinathrin, Alanycarb, Aldoxycarb, Aldrin, Amitraz, Azamethiphos, Bacillus thuringiensis, Phosmet, Phosphamidon, Phosphine, Prallethrin, Propaphos, Propetamphos, Prothoate, Pyraclofos, Pyre, Pyriproxy, Pyrinsafin, Pyrinsafin Quinalphos, RH-7988, Rotenone, Sodiu fluoride, Sodium hexafluorosilicate, Sulfotep, Sulfuryl fluoride, Tar Oils, Teflubenzuron, Tefluthrin, Temephos, Terbufos, Tetrachlorvinphos, Tetramethrin, O-2-tert-Butyl-pyrimidin-5-y isopropyl-phosphorothiate, thiocyclam, thio-fanox, thiometone, tralomethrin, triflumuron, trimethacarb, vamidothion, verticillium lacanii, XMC, xylylcarb, benfuracarb, bensultap, bifenthrin, bioallethrin, isbioophy- lophophenyl (S) -omerophyl-ethyl-bromophenyl (S) -bomophos- thomyl, thiomo- cyclos , Buprofezin, Cadusafos, Calcium Polysulfide, Carbophenothion, Cartap, Chinomethionate, Chlordane, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chloropicrin, Chlorpyrifos, Cyanophos, Beta-Cyfluthrin, AI pha-cy permethrin , Cyophenothrin, Cyro - azine, Dazomet, DDT, Demeton-S-methylsulphon, Diafenthiuron, Dialifos, Dicrotophos, Diflubenzuron, Dinoseb, Deoxabenzofos, Diaxacarb, Disulfoton, DNOC, Empenthrin, Endosulfan, Ethnomethane, EPN , Fenobucarb, Fenoxycarb, Fensulfothion, Fipronil, Flucycloxuron, Flufenprox, Flufenoxuron, Fonofos, Formetanate, Formothion, Fosmethilan, Furthiocarb, Heptachlor, Hexaflumuron, Hydramethylnon, Hydrogen Cyanide, Hydrophosene, Isoprathos, IsoPath Iodfenphos, Kadethrin, Lindane, Malathion, Mecarbam, Mephosfolan, Mercurous, Chloride, Meta, Metarthician, anisopliae, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methoprene, Methoxychlor, Methylisothiocyanate, Metholcarb,

Mevinphos, Monocrotophos, Naled, Neodiprion sertifer NPV, Nicotine, Omethoates, oxydemeton-methyl, pentachlorophenol, petroleum oils, phenothrin, phenthoates, phorates;

Molluscicides:

Fentin acetates, metaldehydes, methiocarb. Niclosamide, thiodicarb, trimethacarb.

Algicides:

Coppersulfate, dichlororphen, Endothal, Fentinacetate, Quinoclamine.

Herbicides: acetochlor, acifluorfen, aclonifen, acrolein, alachlor, alloxydim, ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asula atrazine, aziptrotryne, benazlin, benfluralin, benfuresate, bensulfuron, benzenesulfonon, benzefenzene, benzefenzene, benzefenzene, benzefenzene, benzene, benzene borax, dichlorprop, dichlorprop-P, diclofop, diethatyl, difenoxuron, difenzoquat, diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethipin, dimethylarsinic acid, dinitramine, dinoseb, dinoseb, dinoseb acetate, dinosebomobomilomomolomomom butachlor, butamifos, fuenachlor, butralin, butylate, carbetamide, CGA 184927, chlormethoxyfen, chloramben, chlorbromuron, chlorbutam, chlorfurenol, chloridazon, chlorimuron, chlornitrofen, chloroacetic acid, achloropicrin, chlorotoluron, chloroxuron, chlorprepham, chlorsulfuron, chlorthal, chlorthiamid, cinmethylin, cinofulsuron, clethodim, clomazone, chlomeprop, clopyralid, cyanamide, cyanazine, dinoseb acetate , dinoterb, diphenamid, dipropetryn, diquat, dithiopyr, diduron, DNOC, PPX-A 788, DPX-E96361, DSMA, eglinazine, endothal, EPTC, esprocarb, ethalfl uralin, ethidimuron, ethofumesate, fenoxaprop, fenoxaprop-P, fenuron , flamprop-M, flazasulfuron, fluazifop, fluazifop-P, fluchloralin, flumeturon, fluorocgycofen, fluoronitrofen, flupropanate, flurenol, fluridone, flurochloridone, fluroxypyr, cycloate, cycloxydin, 2,4-D, daimuron, dalap -DB, desmedipham, desmetryn, dicamba, dichlorbenil, isoproturon, isouron, isoxaben, isoxapyrifop, lactofen, lenacil, linuron, LS830556, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, mefenacet, metefazidloride, , methabenzthiazuron, methazole, methoroptryne, methyldymron, methylisothiocyanate, metobromuron, fomosafen, fosamine, furyloxyfen, glufosinate, glyphosate, haloxyfop, hexazinone, imazamethabenz, imazapyr, imazaquin, imazethabyr, prosolysulfolate, iazolynolate ulfuron, pyrazoxyfen, pyributicarb, pyridate, quinclorac, quinmerac, quinocloamine, quizalofop, quizalofop-P, S-23121, sethoxydim, sifuron, simazine, simetryn, SMY 1500, sodium chlorate, sulfometuron, tar oils, TCA, metolachlor, metoxuron, metribzin, metsulfuron, molinolin, monalide , naproanilide, napropamide, naptalam, neburon, nicosulfuron, nipyraclofen, norflurazon, orbencarb, oaryzalin, oxadiazon, oxyfluorfen, paraquat, pebulate, pendimethalin, pentachlorophenol, pentaochlor, petroleum oils, phenmedipham, picloram, piperophos, pretilachlor, primisulfuron, prodi amines, proglinazine, propmeton, prometryn, propachlor, tebutam, tebuthiuron, terbacil, terbumeton, terbuthyiazine, terbutryn, thiazafluoron, thifensulfuron, thiobencarb, thiocarbazil, tiociorim, tralkoxydim, tri-allate, triasyroniphone, tri-sulfuron, tri-sulfuron, tri-sulfuron, 74l , propanil, propaquizafob, propazine, propham.

The weight ratios of the active ingredients in these active ingredient combinations can be varied within relatively large ranges.

The active compound combinations preferably contain the active compound at 0.1 to

99.9%, in particular 1 to 75%, particularly preferably 5 to 50%, the rest being filled 100% by one or more of the above-mentioned mixing partners.

The microbicidal agents or concentrates used to protect the industrial materials contain the active ingredient or combination of active ingredients in a concentration of 0.01 and 95% by weight, in particular 0.1 to 60% by weight.

The application concentrations of the active ingredients or combinations of active ingredients used 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 active substances or agents according to the invention advantageously make it possible to replace the microbicidal agents available hitherto with more effective ones. They show good stability and advantageously have a broad spectrum of activity. The active ingredients are also suitable for use as crop protection agents, in particular as fungicides

Fungicidal agents in crop protection are used to combat plasmodiophoromycetes, Oomycetes, Chytπdiomycetes, Zygomycetes, Asco ycetes, Basidiomycetes, Deuteromycetes

Bactericidal agents are used in crop protection to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteπaceae, Corynebacteπaceae and Streptomycaceae

Some pathogens of fungal and bacterial diseases which come under the generic names listed above may be mentioned as examples, but not by way of limitation

Xanthomonas species, such as, for example, Xanthomonas campestπs pv oryzae,

Pseudomonas species, such as, for example, Pseudomonas syπngae 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 festans,

Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or

Pseudoperonospora cubensis,

Pl as opara species, such as, for example, Plasmopara viticola, Bremia species, such as, for example, Bremia lactucae,

Peronospora species, such as, for example, Peronospora pisi or P brassicae,

Erysiphe species, such as, for example, Erysiphe graminis,

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea,

Podosphaera species, such as, for example, Podosphaera leucotπcha, Ven do a species, such as, for example, Ventuπa inaequalis,

Pyrenophora species, such as, for example, Pyrenophora teres or P graminea

(Conidial form Drechslera, Syn Helminthospoπum),

Cochhobolus species, such as, for example, Coch obolus sativus

(Conidia form Drechslera, Syn Helminthospoπum), Uromyces species, such as, for example, Uromyces appendiculatus,

Puccmia species, such as, for example, Puccinia recondita,

Sclerotinia species, such as, for example, Sclerotinia sclerotiorum,

Ti 11 etia species, such as, for example, Tilletia caπes, Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae, Pellicularia species, such as, for example, Pellicularia sasakii, Pyricularia species, such as, for example, Pyricularia oryzae, Fusarium species, such as, for example, Fusarium culmorum, Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum, Leptosphaeria species, such as, for example, Leptosphaeria nodorum, Cercospora species, such as, for example, Cercospora canescens, Alternaria species, such as, for example, Alternaria brassicae, Pseudocerocosporella species, such as, for example, Pseudocercosporella herpotπ-choides

The fact that the active ingredients are well tolerated by plants in the concentrations required to combat plant diseases enables treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil

The active compounds according to the invention are particularly successful

Control of cereal diseases, such as against Erysiphe, Cochliobolus, and Pyrenophora species or diseases in wine, fruit and vegetable cultivation, such as against Phytophtora and Botrytis species, or also rice diseases, such as Pyricularia species, The active substances according to the invention furthermore have a very strong and broad in vitro

effect on

Depending on their respective physical and / or chemical properties, the active compounds 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, as well as ULV cold and warm fog formulations

These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or

Dispersing agents and / or foaming agents If water is used as an extender, for example. organic solvents can also be used as auxiliary 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 so forth their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohenanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water with liquefied gaseous extenders or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, e.g. aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.For example, natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder e, such as highly disperse, are suitable solid carriers Silica , Aluminum oxide and silicates Possible solid carriers for granules are, for example, broken and fractionated natural rocks such as caicit, 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 stalks. Suitable emulsifiers and / or foam-generating agents are, for example, nonionic and anionic emulsifiers, such as polyoxyethylene en fatty acid esters, polyoxyethylene -Fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates. Suitable dispersants include lignin sulfite leaching and methyl cellulose

Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, and synthetic phospholipids can be used in the formulations. Additional additives can be mineral and vegetable oils

Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes, such as alizine, 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 compounds according to the invention, as such or in their formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, newdicides or insecticides, in order to to broaden the spectrum of activity or to prevent the development of resistance. In many cases, synergistic effects are obtained, i.e. the effectiveness of the mixture is greater than the effectiveness of the individual components

The following compounds can be considered as mixing partners, for example.

Fungicides:

2-aminobutane; 2-anilino-4-methyl-6-cyciopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide; 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyano-phenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino

[alpa- (o-tolyloxy) -o-] yl] 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, Chlozolinat ,, Cufraneb,

Cymoxanil, cyproconazole, cyprofuram,

Dichlorophene, diclobutrazole, diclofluanide, diclomezin, dicloran, diethofencarb

Difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,

Edifenphos, epoxyconazole, ethirimol, etridiazole,

Fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin,

Fenpropimorph, fentin acetate, fentin hydroxide, Ferba, Ferimzone, fluazinam,

Fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl aluminum, fthalides, fuberidazole, furalaxyl,

Furmecyclox,

Guazatine,

Hexachlorobenzene, hexaconazole, hymexazole, Imazalil, imibenconazole, iminoctadine, Iprobefos (EBP), iprodione, isoprothiolan, kasugamycin, copper preparations, such as copper hydroxide, copper naphthenate, copper oxychloride], copper sulfate, copper oxide, oxyne copper and Bordeaux mixture, Mancopper, Mancozeb, Maneb, Meepanipilip Metalaxyl, metconazole, 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, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,

Quintozen (PCNB),

Sulfur and sulfur preparations,

Tebuconazole, tecloftalam, tecnazen, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, trichlamide, tricyclazole, tridemorph, trifluminol, trifluminol

Triticonazole, Validamycin A, Vinclozolin, Zineb, Ziram

Bactericides:

Bronopol, dichlorophene, nitrapyrin, nickel-dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin,

Tecloftalam, 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) - l - (ethoxymethyl - (trifluoromethyI) -lH-pyrrole-3-carbonitrile, Bendiocarb, Benfuracarb, Bensultap, Beta-cyfluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridary, Carbus, Carbophenyl, Cadusafofion, Carbus, Carbos Carbosulfan, Cartap, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, N - [(6-

Chloro-3-pyridinyl) methyl] -N'-cyano-N-methyl-ethanimidamide, chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cyromomethrin, cypermethrin Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron,

Diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion,

Diflubenzuron, dimethoate,

Dimethylvinphos, Dioxathion, Disulfoton, Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox,

Ethoprophos, Etrimphos,

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

Fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate,

Fipronil, Fluazinam, Fluazuron, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenprox, Fluvalinate, Fonophos, Formothion, Fosthiazat, Fubfenprox,

Furathiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox,

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

Ivermectin, llama-cyhalothrin, lufenuron, malathion, mecarbam, mervinphos, mesulfenphos, metaldehyde, methacrifos,

Methamidophos, methidathione, methiocarb, methomyl, metalcarb, milbemectin,

Monocrotophos, moxiectin,

Naled, NC 184, Nitenpyram,

Omethoat, Oxamyl, Oxydemethon M, Oxydeprofos, Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet,

Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenophos,

Promecarb, Propaphos, Propoxur, Prothi ophos, Prothoat, Pymetrozin,

Pyrachlophos, Pyridaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen,

Pyriproxifene, quinalphos,

Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,

Tebufenozide, tebufenpyrad, tebupirimphos, teflubenzuron, tefluthrin,

Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb,

Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomethrin, Triarathen, Triazophos, Triazuron, Trichlorfon, 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 compounds according to the invention, as such, in the form of their customary formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules can be used. They are used in the customary manner, for example by pouring, spraying, atomizing, scattering, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume process or to prepare the active ingredient or the like

Inject active ingredient into the soil yourself. The seeds of the plants can also be treated.

When treating parts of plants, the active compound concentrations in the use forms can be varied within a substantial range: they are 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 of 0.001 to 50 g per kilogram 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% by weight, are required.

The following examples serve to illustrate the invention. The invention is not limited to the examples.

Manufacturing examples

example 1

8.73 g (40 mmol) dimercaptomethylene malononitrile di Na salt are in

60 ml of dimethylformamide (DMF) are introduced and added dropwise with a solution of

7.34 g (40 mmol) of trichloropyrazine in 20 ml of DMF were added. Stir for 3 hours

Room temperature, concentrated and chromatographed the residue over

Silica gel (toluene).

Yield: 6.4 g (Ä 63% of theory),

Mp = 194 ° C.

Analogously to this example and in accordance with the general information given above, the compounds of the formula I listed in Table 1 below are also prepared

Table 1:

Application example

The minimum inhibitory concentrations (MIC) of agents according to the invention are determined to demonstrate the activity against fungi

Example A

Active ingredients according to the invention are added to an agar which is produced using malt extract in concentrations of 0.1 mg / 1 to 5000 mg / 1. After the agar has solidified, it is contaminated with pure cultures of the test organisms listed in Table 1 after 2 weeks of storage at 28 ° C and 60 to 70% relative air humidity, the MIC is determined. MIC is the lowest concentration of active ingredient at which chemical growth occurs due to the type of microbe used; it is shown in Table 3 below

Table 2

The procedure for testing dispersion paints for mold resistance is as follows

The paint to be tested is coated on both sides on a suitable surface In order to obtain practical results, some of the test specimens are leached with running water (24 h, 20 ° C) before the test for mold resistance; another part is treated with a warm fresh air flow (7 days; 40 ° C).

Example B

The test specimens prepared in this way are placed on an agar nutrient medium. The test specimens and nutrient medium are contaminated with fungal spores. After 2 to 3 weeks' storage at 29 + 1 ° C and 80 to 90% rel remains fungus-free or at most shows only a slight infestation

Fungus spores of the following molds, which are known as paint destroyers or are frequently found on paints, are used for contamination

1 Alternaria tenuis

2 Aspergillus flavus

3 Aspergillus niger

4 Aspergillus ustus

5 Cindosporium horbarum

6 Paecilomyces variotii

7 Penicillium citrinum

8 Aureobasidium pullulans

9 Stachybotrys atra Corda

Coatings are resistant to mold in accordance with recipe A (even after leaching and exposure to the wind tunnel) if they contain, for example, 0.6% (based on solids) of compound 15

Recipe A

Exterior emulsion paint based on Acroal 290 D (styrene acrylate)

Trade name parts by weight chemical name

Bayer Titan RKB2 40 titanium dioxide

Talc V58 new 10 magnesium silicate containing water

Durcal 5 45 Caicit CaCO ₃

Walsroder MC 3000 S 2% 30 methyl cellulose Trade name parts by weight chemical name

H, O 6.5 dist. water

Calgon N 10% 3 polyphosphate

Pigment distributor A 10% 1 polyacrylic acid salt

Agitan 281, 1: 1 in Texanol 1

White spirit 5 different aliphatic hydrocarbons

Butyl glycol acetate 1.5 butyl glycol acetate

Acronal 290 D (binders.) 71 polyacrylic acid esters

Total 219.0

Solids content, 135.5 = 61.6%

Example C

Leptosphaeria nodorum test (wheat) / protective

Solvent. 10 parts by weight of N-methyl-pyrrolidone

Emulsifier '0.6 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 efficacy, young plants are used with the preparation of active compound in the stated application rate

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

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. 0% means on

Efficiency that corresponds to that of the untreated control, whereas an efficiency of 100% means that no infection is observed

Example compound no. 2 (Table I) shows an efficiency of 83% at an application rate of 250 g / ha

Table C.

Leptosphaeria nodorum test (wheat) / protective

Example D

Erysiphe test (barley) / protective

Solvent. 10 parts by weight of N-methyl-pyrrolidone

Emulsifier. 0.6 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 dusted with spores from Erysiphe graminis f.sp.hordei

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

Evaluation is carried out 7 days after the inoculation. 0% means on

Efficiency that corresponds to that of the untreated control, whereas an efficiency of 100% means that no infection is observed

Example compound no. 2 (Table 1) shows an efficiency of 84% at an application rate of 250 g / ha

Table D

Erysiphe test (barley) / protective

Example E

Tetranychus test (OP-resistant / immersion treatment)

Solvent: 3 parts by weight

Emulsifier: 1 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 amount of solvent and the stated amount of emulsifier, and the concentrate is diluted to the desired concentration with water containing emulsifier

Bean plants (Phaseolus vulgaris), which are heavily infested with all stages of the common spider mite Tetranychus urticae, are immersed in an active ingredient preparation of the desired concentration

After the desired time, the effect is determined in%. 100% means that all spider mites have been killed; 0% means that none of the spider mites have been killed.

In this test, for example, the compounds 15 of the preparation examples showed a superior activity.

Table E (harmful mites)

Tetranychus test (OP-resistant / immersion treatment)

Active ingredients Active ingredient concentration in% in% after 13 d

According to the invention:

0.1 95

Claims

claims

1. Use of compounds of the general formula (I)

in which

R ¹ and R ² independently of one another represent hydrogen, halogen, alkyl or haloalkyl and

A stands for or

in which

R ³ and R ⁴ independently of one another represent -NO ₂ , -CN, -SO ₂ R ⁵ , -COOR ⁵ , -COR ⁵ and -CONR ⁵ R ⁶ , where

R ^D and R ⁶ independently of one another represent hydrogen, alkyl or aryl,

as microbicides to protect technical materials and plants

2. Compounds of the general formula (I)

YI ^S ^ A (I),

2 ^** ^ ^ Q '

R ² IM ^S

in which R ¹ and R ² independently of one another represent hydrogen, halogen, alkyl or haloalkyl and

A stands for

in which

R ³ and R ⁴ independently of one another represent -NO ₂ , -CN, -SO ₂ R ⁵ , -COOR ⁵ , -COR ⁵ and -CONR ⁵ R ⁶ , where

R ^D and R ⁶ independently of one another represent hydrogen, alkyl or aryl,

except compound 2 (l,

3-dithia-4,7-diazoa-indan-2-ylidenes) - malononitrile

Compounds of the general formula (I) according to Claim 2, in which

R ¹ and R ² independently of one another represent hydrogen, halogen, in each case branched or linear alkyl having 1 to 8 carbon atoms or haloalkyl having 1 to 6 carbon atoms and 1 to 9 identical or different halogen atoms and

stands.

in which

R ³ and R ⁴ independently of one another for -NO ₂ , -CN, -SO _? R ⁵ , -COOR ⁵ , -COR ⁵ and -CONR ⁵ R ⁶ , where R ⁵ and R ⁶ independently of one another represent hydrogen, branched or linear alkyl having 1 to 8 carbon atoms or optionally substituted aryl

4 compounds of general formula (I) according to claim 2, in which

i R ¹ and R ² independently of one another represent hydrogen, chlorine, bromine, fluorine, in each case branched or linear alkyl having 1 to 6 carbon atoms or haloalkyl having 1 to 4 carbon atoms and 1 to 7 fluorine and / or chlorine atoms and

A stands for

in which

R ³ and R ⁴ independently of one another represent -NO ₂ , -CN, -SO ₂ R ⁵ , -COOR ⁵ , -COR ⁵ and -CONR ⁵ R ⁶ , in which

R ⁵ and R ⁶ independently of one another are hydrogen, branched or linear alkyl having 1 to 6 carbon atoms or, if appropriate, 1 to 3 times substituted by halogen, alkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, acyl, acyloxy, CN, NO ₂ Phenyl stands

5 microbicidal agents, characterized by a content of at least one

A compound of formula (I) according to claim 1

0 6 Process for combating microorganisms, characterized in that compounds of the formula (I) according to Claim 1 are allowed to act on microorganisms and / or their habitat

7. A process for the preparation of microbicidal agents, characterized in that compounds of the formulas (I) according to Claims 1 5 to 4 are mixed with extenders and / or surface-active agents Process for the preparation of compounds of the formulas (I) according to

Claim 2, characterized in that pyrazine derivatives of the general formula (II)

in which

R ¹ and R ^{2 have} the meaning given in claim 2 and

Shark represents halogen,

optionally in the presence of diluents and acid binders with salts of the formula (III)

M ^{+ "} S

(in),

M S

in which

A, R ^J , R ⁴ , R ⁵ and R ^{6 have} the meaning given in claim 2 and M ^{+ stands} for a mono- or polyvalent cation