EP0847386A1

EP0847386A1 - N-sulfonyliminodithio compounds useful for plant and material protection

Info

Publication number: EP0847386A1
Application number: EP96930053A
Authority: EP
Inventors: Hermann Uhr; Martin Kugler; Heinrich Schrage
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1995-08-31
Filing date: 1996-08-19
Publication date: 1998-06-17
Also published as: US5925675A; WO1997008140A1; AU6925396A; PL328162A1; KR19990044133A; CN1198736A; JP2000500117A; BR9610297A; DE19532061A1

Abstract

N-sulfonyliminodithio compounds have the formula (I), in which R?1 and R2¿ stand for optionally substituted alkyl, alkenyl or alkinyl, and Ar stands for optionally substituted aryl; also disclosed are processes for preparing these compounds and their use for plant and material protection.

Description

N-SULFONYLIMINODITHIO COMPOUNDS FOR USE IN PLANT AND MATERIAL PROTECTION

The invention relates to new N-sulfonyliminodithio compounds, processes for their preparation and use in plant and material protection.

N-sulfonyliminodialkylthio compounds of a similar structure have been described which are biologically ineffective (R. Gompper; H. Hagele; Chem. Ber. 99, 2885 (1966)).

Structurally similar N-arylsulfonyliminodithio compounds are also known, a biological effect has not been described (M. Hans, H. Dehne,

R. Hartwig; Z. Chem. 26, 204 (1986).

Other N-arylsulfonyliminothiocarboxylic diesters are described as herbicide safeners (EP 1 12 289).

Surprisingly, it has now been found that the new N-sulfonyliminodithio compounds of the general formula (I)

.SO ₂ R

N ^'

S S

in which

R ¹ and R ^{~ represent} optionally substituted alkyl, alkenyl or alkynyl,

and

Ar represents optionally substituted aryl

are excellent for protecting plants and materials.

In addition, new processes for the preparation of N-sulfonyliminodithio compounds of the formula (I) have been found. The new and inventive N-sulfonyliminodithio compounds are generally defined by the formula (I). Compounds of the formula (I) in which

R ¹ and R ² independently of one another are straight-chain and branched alkyl having 1 is 10 carbon atoms, straight-chain or branched alkenyl having 2 to 10 carbon atoms or straight-chain or branched alkynyl having 2 to 10 carbon atoms, each of which is optionally substituted one or more times identically or differently are halogen, alkoxy having 1 to 6 carbon atoms, haloalkoxy having 1 to 6 carbon atoms and 1 to 9 identical or different

Halogen atoms, alkylthio with 1 to 6 carbon atoms, haloalkylthio with 1 to 6 carbon atoms and 1 to 9 identical or different halogen atoms, acyl with 1 to 6 carbon atoms, acyloxy with 1 to 6 carbon atoms, (alkoxy) carbonyl with 1 to 6 carbon atoms, amino , which is optionally identical or differently substituted by alkyl or aryl, optionally substituted phenoxy, aryl, pyridyl or pyridyloxy, nitro or cyano

and

Ar stands for aryl,

which is optionally mono- to pentasubstituted by halogen,

Alkyl with 1 to 10 carbon atoms, haloalkyl with 1 to 8 carbon atoms and 1 to 8 identical or different halogen atoms, alkoxy with 1 to 10 carbon atoms, haloalkoxy with 1 to 8 carbon atoms and 1 to 8 identical or different halogen atoms, alkylthio with 1 to 10 carbon atoms, haloalkylthio with 1 to 8 carbon atoms and 1 to 8 identical or different halogen atoms, amino, monoalkylamino with straight-chain or branched alkyl radicals with 1 to 6 carbon atoms, dialkylamino with identical or different, straight-chain or branched alkyl radicals with 1 each up to 6 carbon atoms, cycloalkyl with 1 to 6 carbon atoms, methylene dioxy, difluoromethylene dioxy, chlorofluoromethylene dioxy, dichloromethylene dioxy, nitro or cyano. Compounds of the formula (I) in which are particularly preferred

R ¹ and R ² independently of one another represent straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched alkenyl having 2 to 8 carbon atoms or straight-chain or branched alkynyl having 2 to 8 carbon atoms, each of which may be one to four times the same or are differently substituted by fluorine, chlorine, alkoxy with 1 to 5 carbon atoms, haloalkoxy with 1 to 5 carbon atoms and 1 to 5 fluorine and / or chlorine atoms, allythio with 1 to 5 carbon atoms, haloalkylthio with 1 to 5 carbon atoms and 1 to 5 fluorine and / or chlorine atoms, acyl with 1 to 5 carbon atoms, acyloxy with 1 to 5 carbon atoms, alkoxycarbonyl with 1 to 5 carbon atoms, amino, which is optionally identical or differently substituted by alkyl with 1 to 4 carbon atoms and / or phenyl, optionally substituted phenoxy, aryl, pyridyl or pyridyloxy, nitro or cyano

and

Ar represents phenyl, which is optionally mono- to tetrasubstituted by fluorine, chlorine, alkyl having 1 to 8 carbon atoms, haloalkyl having 1 to 6 carbon atoms and 1 to 6 fluorine and / or chlorine atoms, alkoxy having 1 to 8 carbon atoms, haloalkoxy with 1 to 6 carbon atoms and 1 to 6 fluorine and / or chlorine atoms, alkylthio with 1 to 8 carbon atoms, haloalkylthio with 1 to 6 carbon atoms and 1 to 6 fluorine and / or chlorine atoms, amino, monoalkylamino with alkyl radicals of 1 to 4 carbon atoms, dialkylamino with the same or different alkyl radicals each with 1 to 4 carbon atoms, cycloalkyl with 1 to 6 carbon atoms, methylenedioxy, difluoromethylenedioxy, chlorofluoromethylenedioxy, dichloromethylenedioxy, nitro or cyano.

R ¹ and R ² very particularly preferably represent methyl, ethyl, n- and i-propyl. n-, s-, i- and t-butyl, allyl and propargyl, which are each optionally substituted and by fluorine and / or chlorine, methoxy or methylthio.

It has been found that the N-sulfonyliminodithio compounds (I) are obtained if sulfonamides of the general formula (II) R'SO ₂ NH ₂ (II)

where R ^{1 has} the meaning given above in the presence of a base with CS, and the salt of the formula (III) formed,

1 Φ where R has the abovementioned meaning and A represents a cation, such as in particular alkali, alkaline earth metal or trialkylammonium ion, first with a compound of the general formula (IV)

R-X (IV)

wherein R ~ has the meaning given above and X represents a leaving group, preferably chlorine, bromine, mesyl, tosyl, and the resulting salt of the formula (V),

wherein R, R ^~ and A have the meanings given above, optionally in the presence of calysers with diazonium salt solutions of anilines of the formula (VI)

H ₂ N-Ar (VI)

where Ar has the meaning given above.

In the reaction sequence, the intermediate stages can either be isolated at each stage or the sequence can be carried out in a one-pot process without purification.

The step of alkylation with (IV) and the reaction with the diazonium salt can also be interchanged in the synthesis sequence. In addition, the compounds of the general formula (I) are also obtained if compounds of the formula (VII),

wherein R, ι and Ar have the meaning given above, optionally in the presence of a base with alkylating agents of the general formula (IV).

The preparation of the salt (III) from (II) with CS ₂ in the presence of a base can be carried out in various solvents depending on the base used. Preference is given to working in water, alcohols, such as methanol, ethanol, butanol, butanol, ketones such as acetone or methyl ethyl ketone, ethers such as dioxane or THF, and also DMSO, DMPU, HMPT, DMF or NMP or mixtures of the

Solvents.

All customary bases can be used as bases. These preferably include tert. Amines such as triethylamine and pyridine; Alkali hydroxides such as sodium and potassium hydroxide; Alkali carbonates and hay bicarbonates such as potassium carbonate and sodium bicarbonate; Alkali and alkaline earth hydrides such as

Sodium hydride and calcium hydride; Alkaline alcoholates such as sodium ethanolate, potassium ethanolate, potassium methoxide, sodium ethanolate.

In general, 2 to 3 equivalents of base are used, but larger excesses are also possible. The reaction temperatures for this reaction step can be varied over a wide range. In general, one works between -30 ° C and + 160 ° C, preferably between -10 ° C and 50 ° C. The reaction can be carried out either under normal pressure or under pressure in an autoclave.

The solvent can be changed to react the salt (III) with (IV) to (V). The solvents already mentioned above for the

Partial step possible. However, it is preferred to continue working in the same solvent without isolating the intermediate. The temperatures of this substep can be varied within a relatively wide range. In general, one works between -30 ° C and + 100 ° C, preferably between -I0 ° C and 50 ° C.

For the next sub-step, which consists in the reaction of (V) with diazonium salts, the solvent can also be changed, although the solvents already mentioned can also be used here. V is preferably not isolated, but the process is continued in the same solvent.

A base and optionally a catalyst and then the diazonium salt solution are preferably added to the solution. The bases already mentioned for the first step can be used as bases, alkali metal hydroxides such as potassium hydroxide or sodium hydroxide are preferably used. All catalysts which require the exchange of the diazonium function for sulfur-containing radicals can be used as catalysts. Cu (I) salts or copper powder are preferably added. The temperature during the addition of the diazonium salt solution can be varied over a wide range. Generally one works between -30 ° C and 60 ° C, preferably between -20 ° C and 40 ° C.

The diazonium salt solution is prepared from anilines using literature methods.

The active compounds according to the invention have a strong microbicidal action and can be used to protect against undesirable microorganisms, such as fungi and bacteria, in crop protection and in the material.

In the present context, materials are to be understood as non-living materials that have been prepared for use in technology. For example, technical materials made by the invention

Active substances are to be protected against microbial change or destruction, adhesives, glue, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials that can be attacked or decomposed by microorganisms. Parts of production plants, for example, are also part of the materials to be protected

Cooling water cycles, which can be impaired by the multiplication of microorganisms. Within the scope of the present invention, technical African materials, preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer fluids.

Bacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can cause degradation or a change in the technical materials. The active substances or agents according to the invention preferably act against bacteria, fungi, in particular mold, 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, such as Trichoderma viride, Escherichia, such as Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa, Staphylococcus, such as Staphylococcus aureus.

Fungicidal agents in crop protection are used to combat plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

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

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 cubense;

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

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

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

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

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 Pyrenophora graminea (conidial form: Drechslera, synonym: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus (conidial form: Drechslera, synonym: Helminthosporium);

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

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

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;

Pyyricularia 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;

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

The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases permits treatment of above-ground parts of plants and also treatment of planting material and seeds and of the soil.

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 are made in a known manner, e.g. 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 foaming agents. If water is used as an extender, e.g. also organic

Solvents are used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, 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 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, 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 calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam-generating 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 dispersants are: eg 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 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 to enlarge the spectrum of action or Achieving special effects such as additional protection against insects can be added. These mixtures can have a broader spectrum of activity than the compounds according to the invention. - II -

In many cases, synergistic effects are obtained, i.e. the effectiveness of the mixture 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, paclobutrazole, penconazole, propioconazole, (±) -cis-l- (4-chlorophenyl) -2 , 2,4-triazol-l-yl) -cycloheptanol, tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole, triticonazole, uniconazole and their metal salts and acid adducts.

Imidazoles such as:

Imazalil, pefurazoate, prochloraz, triflumizole, 2- (l-tert-butyl) -l- (2-chlorophenyl) -3- (l, 2,4-triazol-l-yl) -propan-2-ol, thiazolecarboxanilides 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-fluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxy-acrylate, methyl (E) -2- [2- [6- (2,6-difluorophenoxy) pyrimidin-4-yloxy] phenyl] -3- methoxyacrylates, methyl (E) -2- [2- [3- (pyrimidin-2-yloxy) phenoxy ] phenyl] -3-methoxyacrylates, methyl (E) -2- [2- [3- (5-methylpyrimidin-2-yloxy) phenoxy] phenyl] -3- methoxyacrylates, methyl (E) -2- [ 2- [3- (phenylsulfonyloxy) phenoxy] phenyl] -3-methoxyacrylates, methyl (E) -2- [2- [3- (4-nitrophenoxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2-phenoxyphenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3,5-dimethylbenzoyl) pyrrole-l -yl] -3-methoxyacrylate, methyl (E ) -2- [2- (3-methoxyphenoxy) phenyl] -. 3-methoxyacrylate, methyl (E) -2- [2- (2-phenylethen-l-yl) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3,5-dichlorophenoxy) pyridin-3-yl] -3-methoxyacrylate, methyl (E) -2- (2- (3- (1, 1, 2.2 -tetrafluoroethoxy) p henoxy) phenyl) -3-methoxy-acrylates, methyl (E) -2- (2- [3- (alpha-hydroxybenzyl) phenoxy] phenyl) -3-methoxy-acrylates, methyl (E) -2- (2- (4-phenoxypyridin-2-yloxy) phenyl) -3-methoxyacrylate, methyl (E) -2- [2- (3-n-propyloxyphenoxy) phenyl] 3-methoxyacrylate, methyl (E) -2- [2- ( 3-isopropyloxyphenoxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (2-fluorophenoxy) phenoxy] phenyl] -3-melhoxyacrylate, methyl (E) -2- [2- (3-ethoxyphenoxy) - phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (4-tert-butylpyridin-2-yloxy) phenyI] -3- methoxyacrylate, methyl (E) -2- [2- [3- ( 3-cyanophenoxy) phenoxy] phenyl] -3-methoxy-acrylates, methyl (E) -2- [2- (3-methylpyridin-2-yloxymethyl) phenyl] -3-methoxy-acrylates, methyl (E) -2- [2- [6- (2-methylphenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylates, methyl (E) -2- [2- (5-bromopyridin-2-yloxymethyl) phenyl] -3- methoxy acrylates, methyl (E) -2- [2- (3- (3-iodopyridin-2-yloxy) phenoxy) phenyl] -3-methoxy acrylates, methyl (E) -2- [2- [6- (2-chloropyridin-3-yloxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylates, (E), (E) methyl-2- [2- (5,6-dimethylpyrazin-2-ylmethyloximinomethylthyI) 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-methoxyacrylate, (E) methyl-2- {2- (6- (2-azidophenoxy) pyrimidin-4-yloxy] phenyl} 3-methoxyacrylates, (E), (E) methyl-2- {2- [6-phenylpyrimidin-4-yl) methyloximinomethyl] phenyl} -3-metho xyacrylates, (E), (E) methyl-2-

{2 - [(4-chlorophenyl) methyloximinomethyl] phenyl} -3-methoxyacrylate, (E) methyl- 2- {2- [6- (2-n-propylphenoxy) -1,3,5-triazine-4- yloxy] phenyl} -3-methoxyacrylates,

(E), (E) methyl-2- {2 - [(3-nitrophenyl) methyloximinomethyl] phenyl} -3-methoxyacrylate;

Succinate dehydrogenase inhibitors such as:

Fenfuram, furcarbanil, cyclafluramide, 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 dichlofluanid, tolylfluanid, folpet, fluorfolpet; Captan, Captofol;

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

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

Dodemorph, aldimorph, fenpropidine and their arylsulfonic acid salts such as e.g. p-toluenesulfonic acid and p-dodecylphenyl sulfonic acid;

Dithiocarbamate, Cufraneb, Ferbam, Mancopper, Mancozeb, Maneb, Metam,

Metiram, Thiram Zeneb, Ziram;

Benzothiazoles such as 2-mercaptobenzothiazole;

Benzamides such as 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; Boron compounds such as boric acid, boric acid ester, borax; Formaldehyde and formaldehyde-releasing compounds such as benzyl alcohol mono- (poly) -hemiformal, oxazolidines, hexa-hydro-S-triazines, N-methylolchloroacetamide, paraformadehyde, nitropyrin, oxolinic acid, tecloftalam;

Tri s-N- (cy cl ohexy 1 di azeni umdi oxy) aluminum, N- (Cy cl o-hexyl di azeni um di oxy) - tributyltin or K salts, bis-N- (cyclohexyldiazeniumdioxy) copper;

N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, N-octyl-isothiazolin-3-one, 4,5- Trimethylene-isothiazolinone, 4,5-benzisothiazolinone, N-methylolchloroacetamide;

Aldehydes such as cinnamaldehyde, formaldehyde, glutardialdehyde, β-bromocinnamaldehyde; Thiocyanates such as thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate, etc; quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylam onium chloride, didecyldimethaylammonium chloride; Iodine derivatives such as diiodomethyl p-tolyl sulfone, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenylethyl carbamate, 2,3,3-triiodo allyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl-n-butyl carbamate, 3-iodo-2-propynyl-n-hexyl carbamate, 3-iodo-2-propynyl cyclohexyl carbamate, 3-iodo-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

Erdal kal i 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- (2nd , 4,4-trimethylpentyl) -2 (1H) pyridine;

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

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

Oxides such as tributyltin oxide, Cu, 0, 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-cyano-vinyl) sulfone,

Phenyl- (1,2-dichloro-2-cyano-vinyl) sulfone;

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

Active ingredients.

Mixtures with azaconazole, bromuconazole, cyproconazole, dichlobutrazole, diniconazole,

Hexaconazole, metaconazole, penconazole, propiconazole, tebuconazole, methyl- (E) -methoximino [α- (o-tolyloxy) -o-tolyl)] acetate, methyl - (E) -2- {2- [6- (2- cyanophenoxy) pyrimidin-4-yl-oxy] phenyl} -3-methoxyacrylate, methfuroxam, carboxin, fen- piclonil, 4- (2,2-difluoro-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, diethyl dicarbonate, and / or 3-iodo-2-propynyl-n-butyl carbamate.

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

Fungicides:

Acypetacs, 2-aminobutane, Ampropylfos, anilazine, benalaxyl, Bupirimate, chinomethionat, chloroneb, chlozolinate, cymoxanil, dazomet, Diclomezine, Dichloram, diethofencarb, dimethirimol, Diocab, dithianon, dodine, Drazoxolon, edifenphos, ethirimol, etridiazole, fenarimol, Fenitropan, Fentin acetate, Fentin

Hydroxide, Ferimzone, Fluazinam, Fluromide, Flusulfamide, Flutriafol, Fosetyl, Fthalide, Furalaxyl, Guazatine, Hymexazol, Iprobefos, Iprodione, Isoprothiolane, Metalaxyl, Methasulfocarb, Nitrothal-isopropyl, Nuarimol, Ofurace- Pourduryl, Oxaduryl, Oxad Pimaricin, piperalin, procymidone, prop amocarb, Propineb, Pyrazophos, Pyrifenox, Pyroquilon, Quintozene, Tar Oils, Tecazene, Thicyofen, Thiophanate-methyl, Tolclofos-methyl, Triazoxide, Trichlamide, Tricyclazole, Triforine, Vinclozolin.

Insecticides: phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, α-1 (4-chlorophenyl) -4-

(O-ethyl, S-propyl) phosphoryloxy-pyrazole, Chlorpyrifos, Coumaphos, Demeton, Demeton-S-methyl, Diazinon, Dichlorvos, Dimethoate, Ethoate, Ethoprophos, Etrimfos, Fenitrothion, Fenthion, Heptenophas, Parathion, Parathion-methyl, Phosalone , Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothiofos, Sulfprofos, Triazophos and Trichlorphon;

Carbamates such as aldicarb, bendiocarb, α-2- (l-methylpropyl) phenylmethyl carbamate, butocarboxime, butoxycarboxime, carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarb; Organosilicon compounds, preferably dimethyl (phenyl) silylmethyl-3-phenoxybenzyl ether such as dimethyl (4-ethoxyphenyl) silylmethyl-3-phenoxybenzyl ether or

(Dimethylphenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether such as e.g. Dimethyl- (9-ethoxy-phenyl) -silylmethyl-2-phenoxy-6-pyridylmethylether or [(phenyl) -3- (3-phenoxyphenyl) -propyl] (dimethyl) -silanes such as e.g. (4-ethoxyphenyl) - [3- (4-fluoro-3-phenoxyphenyl-propyl-dimethyl-silane, silafluofen;

Pyrethroids such as Allethrin, Alpha ethrin, 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-lH-imidazol-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,

Phosphines, prallethrin, propaphos, propetamphos, Prothoate, Pyraclofos, Pyre thrins, pyridaben, pyridafenthion, pyriproxyfen, quinalphos, RH-7988, rotenone, sodium fluoride, sodiu hexafluorosilicate, sulfotep, sulphuryl fluoride, tar Oils, teflubenzuron, tefluthrin, temephos, Terbufos, Tetrachlorvinphos, Tetramethrin, O-2-tert.-Butyl-pyrimidin-5-yl-o-isopropyl-phosphorothiate, Thiocyclam, Thiofanox, Thiometon, Tralomethrin, Triflumuron, Trimethacarb, Vamidothion, Verti- cillium Lacanii, XMC, Xylylcarb, Benfuracarb, Bensultap, Bifenthrin, Bioallethrin, MERbioallethrin (S) -cyclopentenyl isomer, Bromophos, Bromophos-ethyl, Buprofezin, Cadusafos, Calcium Polysulfide, Carbophenothion, Chlorofluorononethonon Chlormephos, Chloropicrin, Chlorpyrifos, Cyanophos, Beta-Cyfluthrin, Alpha-cypermethrin, Cyophenothrin, Cyromazine, Dazomet, DDT, Demeton-S-methylsulphon, Diafenthiuron, Dialifos, Di-crotophos, Diflofebosuron, Diflubebosuron Disulfoton, DNOC, Empenthrin, Endosulfan, EPN, Esfenvalerate, Ethiofencarb, Ethion, Etofenprox, Fenobucarb, Fenoxycarb, Fensulfothion, Fipronil, Flucycloxuron, Flufenprox, Flufenoxuron, Fonofos, Formetanate, Formothion, Fosmethachonuron, fosmethilonuron, f Hydrogen Cyanide, Hydropene, IPSP, Isazofos, Isofenphos, Isoprothiolane, Isoxathion, Iodfenphos, Kadethrin, Lindane, Malathion, Mecarbam, Mephosfolan, Mercurous, chloride, M etam, metarthic, anisopliae, methacrifos, methami dophos, methidathione, methiocarb, methoprene, methoxychlor, methyl isothiocyanate, metholcarb,

Mevinphos, Monocrotophos, Naled, Neodiprion sertifer NPV, Nicotine, Omethoate, Oxydemeton-methyl, Pentachlorophenol, Petroleum oils, Phenothrin, Phenthoate, Phorate;

MoIIuscicide: fentin acetates, metaldehydes, methiocarb. Niclosamide, thiodicarb, trimethacarb.

Algicide:

Coppersulfate, dichlororphen, Endothal, Fentinacetate, Quinoclamine.

Herbicides:

acetochlor, acifluorfen, aclonifen, acrolein, alachlor, alloxydim, ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam atrazine, aziptrotryne, benazolin, benfluralin, benfuresate, bensulfuron, bensulfide, benzafthoxane, benzafone, benzafone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzazone, benzafone, benzazone, benzazone benzax dichlorprop, dichlorprop-P, diclofop, diethatyl, difenoxuron, difenzoquat, diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethipin, dimethylarsinic acid, dinitramine, dinoseb, dinoseb, dinoseb acetate, dinoseb, bromynoxoxiloxyloxomiloxilyl, bromomoxililoxyl bromoboxane butamifos, fuenachlor, butralin, butylates, carbetamides, CGA 184927, chloromethoxyfen, chloramben, chlorbromuron, chlorobutam, chlorofurenol, chloridazon, chlorimuron, chloronitrofen, chloroacetic acid, achloropicrin, chlorotoluron, chloroxuron, chlorprepham, chlorsulfuron, chlorthal, chlorthiamid, cinmethylin, cinofulsuron, clethodim, clomazone, clomeprop, clopyralid, cyanamide, cyanazine, dinoseb acetate, dinoterb, diphonamid, dyrenyridyl, dyrenyridyl, dyrenyridyl, dyrenitrid, dyrenyl dyrenyl, dyrenyl, dyrenyl PPX-A 788, DPX-E96361, DSMA, eglinazine, endothal, EPTC, esprocarb, ethalfluralin, ethidimuron, ethofumesate, fenoxaprop, fenoxaprop-P, fenuron, flamprop, flamprop-M, flazasulfuron, fluazifop, fluazifalin-P, fluchetloron-P, , fluorocgycofen, fluoronitrofen, flupropanate, flurenol, fluridone, flurochloridone, fluoroxypyr, cycloate, cycloxydim, 2,4-D, dai uron, dalapon, dazomet, 2,4-DB, desmedipham, desmetryn, dicamba, dichlorbenil, isoproturon, isouron isoxaben, isoxapyrifop, lactofen, lenacil, linuron, LS830556, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, mefenacet, mefluidide, metam, metamitron, metazachlor, methabenzthiazuron, methazole, methopropronne, methyl. methyl ocyanate, metobromuron, fomosafen, fosamine, furyloxyfen, glufosinate, glyphosate, haloxyfop, hexazinone, imazamethabenz, imazapyr, imazaquin, imazethapyr, ioxynil, isopropalin, propyzamide, prosulfocab, pyrazolynin, pyibolocin quinocurin, pyribosquin quinocurin, pyrazole quinoxin, pyrazole quinocurin, pyrazole quinocurin, pyrazole quinocurin, pyrazole quinoxin, pyrazole quinocurin, pyrazole quinocurin, pyrazole quinocurin, pyrazole quinoxin quizalofop, quzizalofop-P, S-23121, sethoxydim, sifuron, simazine, simetryn, SMY 1500, sodium chlorate, sulfometuron, tar oils, TCA, metolachlor, metoxuron, metribzin, metsulfuron, molinate, monalide, monolinuran, MSMA, napro amide , naptalam, neburon, nicosulfuron, nipyraclofen, norflurazon, orbencarb, oaryzalin, oxadiazon, oxyfluorfen, paraquat, pebulate, pendimethalin, pentachlorophenol, pentaochlor, petroleum oils, phenmedipham, picloram, piperophos, prisulfonlin, prisulfonol, prodiline chlorine propachlor, tebutam, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutryn, thiazafluoron, thifensulfuron, thiobencarb, thiocarbazil, tioclorim, tralkoxydim, tri-allate, triasulfuron, tribenzuron, triclopyr, tridiphane, trietazine, trifluralin, IBI-C4874 vernolate, propanil, propaquizafop, propazine, propham.

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 from 0.1 to 99.9%, in particular from 1 to 75%, particularly preferably from 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 to be 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 to date with more effective and less toxic ones. They show good stability and advantageously have a broad spectrum of activity.

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

Manufacturing examples

example 1

9.5 g (0.1 mol) of methyl sulfonamide are placed in DMF and, with vigorous stirring, a solution of 4 g of NaOH in 6 ml of H 0 is added. 3.3 ml of CS _{2 are added} dropwise to the thick, white suspension. After a stirring time of 10 min, a solution of 2 g NaOH in 3 ml H ₂ O and then 1.9 ml CS _{2 is} added. The process is repeated again after 10 minutes. 14.2 g (0.1 mol) of methyl iodide are added dropwise to the red solution obtained here with cooling. After stirring for about 2 hours, 50 ml of 20% KOH and 7 g of Cu powder are added to the resulting suspension. After cooling to 0 to 5 ° C., the diazonium salt solution I (see below) is added dropwise. The mixture is stirred for 2 h, suction filtered, washed with H-, 0 and the soluble constituents of the residue are taken up in ethyl acetate. After drying over Na ₂ SO ₄ , the mixture is concentrated and chromatographed on silica gel (toluene).

Yield 6.5 g (22% of theory). Physical constants see Table 1.

Diazonium salt solution I:

13.3 g (0.1 mol) of p-anisides are placed in 180 ml of H, 0 and 25 ml of concentrated HCL at 2 ° C., with a solution of 7.3 g of NaNO ₂ in 60 ml of H-, 0 dropwise added and stirred for 1 h.

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

(N-sulfonyliminodifhio compounds I)

.SO ₂ R ¹

N ^'

, Ar s s

22

- 23

Examples of use

To demonstrate the effectiveness against fungi, the minimum inhibitory concentrations (MIC) of agents according to the invention are determined:

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 5,000 mg / 1. After the agar solidifies, 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 humidity, the MIC is determined. MIC is the lowest concentration of active ingredient at which no growth occurs due to the type of microbe used, it is shown in Table 2 below.

Table 2 Minimum inhibitory concentrations (ppm) of the invention

Compounds of formula (I)

Example No. 2 3 comparison compound *

from EP 1 12 289 p. 18 Example No. 3

H ₃ C

Claims

claims

1. Compounds of the general formula (I)

.SO _? R ¹ N

in which

R ¹ and R ^{2 represent} optionally substituted alkyl, alkenyl or alkynyl,

and

Ar represents optionally substituted aryl.

2. Compounds of formula (I) according to claim 1, in which

R ¹ and R ² independently of one another are straight-chain and branched alkyl having 1 is 10 carbon atoms, straight-chain or branched alkenyl having 2 to 10 carbon atoms or straight-chain or branched alkynyl having 2 to 10 carbon atoms, each of which is optionally substituted one or more times identically or differently are halogen, alkoxy with 1 to 6 carbon atoms, halogeno-alkoxy with 1 to 6 carbon atoms and 1 to 9 identical or different halogen atoms,

Alkylthio with 1 to 6 carbon atoms, haloalkylthio with 1 to 6 carbon atoms and 1 to 9 identical or different halogen atoms, acyl with 1 to 6 carbon atoms, acyloxy with 1 to 6 carbon atoms, (alkoxy) carbonyl with 1 to 6 carbon atoms, amino , which is optionally identical or differently substituted by alkyl or aryl, optionally substituted phenoxy, aryl, pyridyl or pyridyloxy, nitro or cyano

and

Ar stands for aryl, which is optionally mono- to pentasubstituted by halogen, alkyl having 1 to 10 carbon atoms, haloalkyl having 1 to 8 carbon atoms and I to 8 identical or different halogen atoms, alkoxy having 1 to 10 carbon atoms, haloalkoxy having 1 to 8 carbon atoms and 1 up to 8 identical or different halogen atoms, alkylthio with 1 to 10 carbon atoms, haloalkylthio with 1 to 8 carbon atoms and 1 to 8 identical or different halogen atoms, amino, monoalkylamino with straight-chain or branched alkyl radicals with 1 to 6 carbon atoms, dialkylamino with the same or various straight-chain or branched alkyl radicals each having 1 to 6 carbon atoms, cycloalkyl having 1 to 6 carbon atoms, methylene-dioxy, difluoromethylene-dioxy, chlorofluoromethylene-dioxy, dichloromethylene-dioxy, nitro or cyano.

Compounds of formula (I) in which

R ¹ and R ² independently of one another represent straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched alkenyl having 2 to 8 carbon atoms or straight-chain or branched alkynyl having 2 to 8 carbon atoms, each of which may be one to four times the same or are differently substituted by fluorine, chlorine, alkoxy with 1 to 5 carbon atoms, haloalkoxy with 1 to 5 carbon atoms and 1 to 5 fluorine and / or chlorine atoms, allythio with 1 to 5 carbon atoms, haloalkylthio with 1 to 5 carbon atoms and 1 to 5 fluorine and / or chlorine atoms, acyl with 1 to 5 carbon atoms, acyloxy with 1 to 5 carbon atoms, alkoxycarbonyl with 1 to 5 carbon atoms, amino, which is optionally identical or differently substituted by alkyl with 1 to 4 carbon atoms and / or phenyl, optionally substituted phenoxy, aryl, pyridyl or pyridyloxy, nitro or

Cyano, stands

and Ar represents phenyl, which is optionally mono- to tetrasubstituted by fluorine, chlorine, alkyl having 1 to 8 carbon atoms, haloalkyl having 1 to 6 carbon atoms and 1 to 6 fluorine and / or chlorine atoms, alkoxy with 1 to 8 Koh - lenstoffatomen, haloalkoxy with 1 to 6 carbon atoms and

1 to 6 fluorine and / or chlorine atoms, alkylthio with 1 to 8 carbon atoms, haloalkylthio with 1 to 6 carbon atoms and 1 to 6 fluorine and / or chlorine atoms, amino, monoalkylamino with alkyl radicals of Λ to 4 carbon atoms , Dialkylamino with the same or different alkyl radicals each with 1 to 4 carbon atoms, cycloalkyl with 1 to 6 carbon atoms, methylenedioxy, difluoromethylenedioxy, chlorofluoromethylenedioxy, dichloromethylenedioxy, nitro or cyano.

4. pesticides, characterized by a content of at least one compound of the formula (I) according to claim 1.

5. A method for controlling pests, characterized in that compounds of the formula (I) according to Claim 1 are allowed to act on pests and / or their habitat.

6. Use of compounds of the formula (I) according to claims 1 to 3 for combating pests in plants and material.

7. A process for the preparation of pesticides, characterized in that compounds of the formula (I) according to Claims 1 to 3 are mixed with extenders and / or surface-active agents.

8. A process for the preparation of compounds of formula (I) according to claim 1, characterized in that

a) sulfonamides of the general formula (II)

R'SO ^ NH-, (II) where R ^{1 has} the meaning given in claim 1 in the presence of a base with CS ₂ and the resulting salt of the formula (III),

where R ^{1 has} the meaning given above and A® represents a cation, first with a compound of the general formula (IV)

. ~>

R-X (IV)

where R "has the meaning given in claim 1 and X represents a leaving group, brings about the reaction and the resulting salt of the formula (V),

where R ¹ , R ² and A have the meanings given above, if appropriate in the presence of analyzers with diazonium salt solutions from anilines of the formula (VI)

H ₂ N-Ar (VI)

where Ar has the meaning given in claim 1, or b) compounds of the formula (VII),

wherein R ¹ and Ar have the meanings given in claim 1, if appropriate in the presence of a base, with alkylating agents of the general formula (IV).