AU7763998A - Pyridylthio-dithiazole dioxide derivatives and their use as pesticides - Google Patents

Description

PYRIDYLTHIO-DITHLAZOLE DIOXIDE DERIVATIVES AND THEIR USE AS PESTICIDES 5 The invention relates to new S-pyridyl-dithiazole dioxides, to processes for their preparation, and to their use in the protection of plants and materials. Dithiazoles with a 5-membered ring have already been described, but a biological effect is not mentioned (see K. Dickor6, Lieb. Ann. Chem. 671 (1964); US-PA 3 345 10 374). S-Aryldithiazole dioxides have been disclosed, but their spectrum of action does not reach the required level, especially as regards the bactericidal action (see DE 19 545 635). There have also been described dithiazine oxides (6-membered rings) which are alkyl-substituted on the S, but a biological effect is not mentioned (see Nakahashi et al., Bull. Chem. Soc. Jpn. 4, 3217 (1972); Hasegawa, K. et al., Bull. 15 Chem. Soc. Jpn. 45, 1567 (1972)). Surprisingly, it has now been found that the new compounds of the general formula (I) N-SO 20 Pyr-S S CH2)n (I in which Pyr represents D )llFR 1 4'1N-4 WAr oa- -2 N NN , N N which is optionally mono- or disubstituted and 5 n represents I or 2, are outstandingly suitable for the protection of plants and materials. Preferred compounds of the formula (I) are those in which Pyr is optionally mono- to 10 pentasubstituted by halogen, alkyl having 1 to 10 carbon atoms, halogenoalkyl having I to 8 carbon atoms and I to 8 identical or different halogen atoms, alkoxy having 1 to 10 carbon atoms, halogenoalkoxy having 1 to 8 carbon atoms and I to 8 identical or different halogen atoms, alkylthio having 1 to 10 carbon atoms, halogenoalkylthio having 1 to 8 carbon atoms and 1 to 8 identical or different 15 halogen atoms, amino, monoalkylamino having straight-chain or branched alkyl radicals having 1 to 6 carbon atoms, dialkylamino having identical or different straight-chain or branched alkyl radicals, each of which has 1 to 6 carbon atoms, cycloalkyl having I to 6 carbon atoms, methylenedioxy, difluoromethylenedioxy, chlorofluoromethylenedioxy, dichloromethylenedioxy, nitro, cyano or the radical 20 7q RA4,, -U LAr 4j -3

H

3 C N S- N

CH

3 Especially preferred compounds of the formula (I) are those in which Pyr is 5 unsubstituted or mono- to tetrasubstituted, preferably mono- to disubstituted, by fluorine, chlorine, bromine, alkyl having 1 to 8 carbon atoms, preferably methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, halogenoalkyl having 1 to 6 carbon atoms and 1 to 6 fluorine and/or chlorine atoms, preferably trifluoromethyl, trifluoroethyl, difluorochloromethyl, alkoxy having 1 to 8 carbon atoms such as, preferably, 10 methoxy, ethoxy, u- or i-propoxy, n-, i-, s- or t-butoxy, halogenoalkoxy having 1 to 6 carbon atoms and 1 to 6 fluorine and/or chlorine atoms such as, preferably, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, alkylthio having 1 to 8 carbon atoms, halogenoalkylthio having 1 to 6 carbon atoms and 1 to 6 fluorine and/or chlorine atoms, amino, monoalkylamino having alkyl 15 radicals of 1 to 4 carbon atoms, dialkylamino having identical or different alkyl radicals, each of which has I to 4 carbon atoms, cycloalkyl having 1 to 6 carbon atoms, methylenedioxy, difluoromethylenedioxy, chlorofluoromethylenedioxy, dichloromethylenedioxy, nitro, cyano or

H

3 C N S- NN 20 C H 3 and n represents 1 or 2. 25 Particularly preferred compounds of the formula (I) are those in which Pyr represents SRAZp unsubstituted and substituted groups of the formula rr 441 -TqDO' -4 or N ON The definitions of radicals given in detail for these radicals in the particular 5 combinations, or preferred combinations, of radicals are also replaced by definitions of radicals of other preferred ranges, if so desired, independently of the combination given in each case. Moreover, it has been found that the compounds of the formula (I) are obtained when 10 the salts of the general formula (II) ,so (C

H

2 )' _ S in which 15 n represents 1 or 2, M9 represents an alkali metal ion or alkaline earth metal ion, in particular Na+, K+, 20 are reacted with diazonium salts of the general formula (III) Pyr-N=NOAO (III) 25 in which Pyr has the abovementioned meaning and vT

A

9 represents the anion of a mineral acid in aqueous/alkaline solution, if appropriate in the presence of a catalyst. 5 It is preferred to add a base and, if appropriate, a catalyst to a solution of (II), followed by the diazonium salt solution (III). The bases employed are preferably alkali metal hydroxides such as, for example, potassium hydroxide or sodium hydroxide. Catalysts which can be employed are all those catalysts which promote 10 the exchange of the diazonium function for sulphur-containing radicals. It is preferred to employ Cu(I) salts or copper powder. The temperature during addition of the diazonium salt solution can be varied within a broad range. In general, the process is carried out at between -30'C and +60*C, preferably at between -20 0 C 15 and +40'C. The diazonium salt solution is prepared from anilines following methods known from the literature. The salts of the general formula (II) are known in some cases or can be prepared analogously to methods known from the literature (see references p.1). Either salts of 20 the formula (II) which have been isolated in solid form or solutions prepared in situ can be employed. Moreover, it has been found that the compounds of the formula (I) are also obtained when the new compounds of the general formula (IV) 25 So N 7 (CH2)n (IV) in which N> Y ; ' -6 n represents 1 or 2 are reacted with thio compounds of the general formula (V) 5 Pyr-SH (V) in which Pyr has the abovementioned meaning, 10 if appropriate in the presence of bases or diluents. When carrying out this process, the reaction temperatures can be varied within a substantial temperature range. In general, the process is carried out at between -30*C 15 and 100*C, preferably at between -10 C and +60'C. If appropriate, the reactions are carried out in the presence of bases, and all customary bases can be employed for this purpose. These preferably include tertiary amines such as triethylamine and pyridine; alkali metal hydroxides such as sodium 20 hydroxide and potassium hydroxide, and alkali metal carbonates and alkali metal hydrogencarbonates such as potassium carbonate and sodium hydrogencarbonate. Suitable diluents which are optionally used are water, but also all inert organic solvents. These preferably include hydrocarbons such as toluene, xylene or hexane, 25 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, and DMSO, DMF and NMP. The compounds of the general formula (IV) can be prepared when compounds of the 30 general formula (VI) ~44 'A(- Op" -7 "so SO2 N N R(CH2)n (VI) R--S S where 5 R represents alkyl are reacted with halogenating agents, if appropriate in the presence of diluents. R preferably represents alkyl having I to 5 carbon atoms; 10 especially preferably methyl-, ethyl-, propyl-, isopropyl, butyl, isobutyl or sec-butyl. In this process, the reaction temperatures can be varied within a substantial temperature range. In general, the process is carried out at between -30'C and 120*C, 15 preferably at between -0I 0C and 100'C. Preferred diluents which can optionally be employed are chlorinated hydrocarbons such as, for example, carbon tetrachloride, chloroform, methylene chloride or 1,2-dichloroethane. The compounds of the general formula (VI) are known or can be prepared by known 20 processes (see US-PA 3 345 374). All customary halogenating agents can be used as halogenating agents. Preferred halogenating agents are chlorine, bromine, sulphuryl chloride. 25 The active compounds according to the invention have a potent microbicidal action and can be employed in the protection of plants and materials for controlling 11 FRIAI undesired microorganisms, preferably fungi and bacteria. _j) 0T -8 Industrial materials in the present context are understood as meaning non-live materials which have been prepared for use in industry. For example, industrial materials which are intended to be protected by active compounds according to the invention from microbial change or destruction can be glues, sizes, paper and board, 5 textiles, leather, wood, paints and synthetic articles, cooling lubricants and other materials which can be infected with, or destroyed by, microorganisms. Parts of production plants, for example cooling-water circuits, which may be impaired by the multiplication of microorganisms may also be mentioned within the scope of the materials to be protected. Industrial materials which may be mentioned within the 10 scope of the present invention are preferably glues, sizes, papers and boards, leather, wood, paints, cooling lubricants and heat transfer liquids. Examples of microorganisms which are capable of bringing about degradation of, or change in, the industrial materials and which may be mentioned are bacteria, fungi, 15 yeasts, algae and slime organisms. The active compounds or compositions according to the invention preferably act against fungi, in particular moulds, and against slime organisms and algae. Microorganisms of the following genera may be mentioned by way of example: 20 Altemaria, such as Alternaria tenuis, Aspergillus, such as Aspergillus niger, Chaetomium, such as Chaetomium globosum, Coniophora, such as Coniophora puetana, Lentinus, such as Lentinus tigrinus, 25 Penicillium, such as Penicillium glaucum, Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aurcobasidium pullulans, Sclerophoma, such as Sclerophoma pityophila, Trichoderma, such as Trichoderma viride, 30 Escherichia, such as Escherichia coli, 3 RA4, Pseudomonas, such as Pseudomonas aeruginosa, 41- -9 Staphylococcus, such as Staphylococcus aureus. Fungicidal compositions in crop protection are employed for controlling Plasmo diophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basi 5 diomycetes, Deuteromycetes. A few pathogens of fungal diseases which come under the generic name listed above may be mentioned as examples, but not by way of limitation: 10 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 15 Pseudoperonospora cubense; Plasmopara species, such as, for example, Plasmopara viticola; Peronospora species, such as, for example, Peronospora pisi or Peronospora 20 brassicae; Erysiphe species, such as, for example, Erysiphe graminis; Sphaaerotheca species, such as, for example, Sphaerotheca fuliginea; 25 Podosphaera species, such as, for example, podosphaera leucotricha; Venturia species, such as, for example, Venturia inacqualis; 30 Pyrenophora species, such as, for example, Pyrenophora teres or Pyrenophora graminea (conidia form: Drechslera, syn: Helminthosporium); -10 Cochliobolus species, such as, for example, Cochliobolus sativus (conidia form: Drechslera, syn: Helminthosporium); 5 Uromyces species, such as, for example, Uromyces appendiculatus; Puccinia species, such as, for example, Puccinia recondita; Tilletia species, such as, for example, Tilletia caries; 10 Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae; Pellicularia species, such as, for example, Pellicularia sasakii; 15 Pyricularia species, such as, for example, Pyricularia oryzae; Fusarium species, such as, for example, Fusarium culmorum; Botrytis species, such as, for example, Botrytis cinerea; 20 Septoria species, such as, for example, Septoria nodorum; Leptosphaeria species, such as, for example, Leptosphaeria nodorum; 25 Cercospora species, such as, for example, Cercospora canescens; Alternaria species, such as, for example, Altemaria brassicae; Pseudocercosporella species, such as, for example, Pseudocercosporella herpotri 30 choides. VTJ0 - 11 The fact that the active compounds are well tolerated by plants also permits the treatment of plants at the concentrations required for controlling plant diseases, thereby permitting the treatment of aerial parts of plants, of propagation stock and seeds, and of the soil. 5 Depending on their particular physical and/or chemical properties, the active compounds of the formula (1) can be converted to the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and microencapsulations in polymeric substances. 10 These formulations or compositions are produced in a known manner, for example by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surfactants, that is, emulsifiers and/or dispersants, and/or foam formers. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. 15 The following are mainly suitable as liquid solvents: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example mineral oil fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such 20 as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulphoxide, or else water; liquefied gaseous extenders or carriers are to be understood as meaning liquids which are gaseous at ambient temperature and under atmospheric pressure, for example aerosol propellants such as halogenohydrocarbons, or else butane, propane, nitrogen 25 and carbon dioxide; suitable solid carriers are: for example ground natural minerals, such as kaolins, clays, tale, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as highly-disperse silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable - 12 emulsifiers and/or foam formers are: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, or else protein hydrolysates; suitable dispersants are: for example 5 lignin-sulphite waste liquors and methylcellulose. Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other additives can be 10 mineral and vegetable oils. It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc. 15 The efficacy and the spectrum of action of the active compounds of the formula (I), or the compositions, precursors or, quite generally, formulations which can be prepared from them can be increased when, if appropriate, other antimicrobially active compounds, fungicides, bactericides, herbicides, insecticides or other active compounds for widening the spectrum of action or achieving specific effects such as, 20 for example, an additional protection from insects, are added. These mixtures may have a broader spectrum of action than the compounds according to the invention. In many cases, synergistic effects result, i.e. the efficacy of the mixture exceeds the efficacy of the individual components. Examples of particularly advantageous components in mixtures are the following compounds: 25 Triazoles such as: azaconazole, azocyclotin, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, epoxyconazole, etaconazole, fenbuconazole, R ~fenchlorazole, fenethanil, fluquinconazole, flusilazole, flutriafol, furconazole, 77 hexaconazole, imibenconazole, ipconazole, isozofos, myclobutanil, metconazole, - 13 paclobutrazol, penconazole, propioconazole, (±)-cis- 1 -(4-chlorophenyl)-2-(l H- 1,2,4 triazol-1-yl)-cycloheptanol, 2-(1-tert-butyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl) propan-2-ol, tebuconazole, tetraconazole, triadimefon, triadimenol, triapenthenol, tri flumizole, triticonazole, uniconazole and their metal salts and acid adducts; 5 Imidazoles such as: clotrimazole, bifonazole, climbazole, econazole, fenapamil, imazalil, isoconazole, ketoconazole, lombazole, miconazole, pefurazoate, prochloraz, triflumizole, thia zolcar, 1-imidazolyl-1-(4'-chlorophenoxy)-3,3-dimethylbutan-2-one, and their metal 10 salts and acid adducts; Pyridines and pyrimidines such as: ancymidol, buthiobate, fenarimol, nuarimol, triamirol; 15 Succinate dehydrogenase inhibitors such as: benodanil, carboxim, carboxim sulfoxide, cyclafluramid, fenfuram, flutanil, furcarb anil, furmecyclox, mebenil; mepronil, methfuroxam, metsulfovax, pyrocarbolid, oxycarboxin, shirlan, Seedvax; 20 Naphthalene derivatives such as: terbinafine, naftifine, butenafine, 3-chloro-7-(2-aza-2,7,7-trimethyl-oct-3-en-5-ine); Sulfenamides such as: dichlorofluanid, tolylfluanid, folpet, fluorofolpet; captan, captofol; 25 Benzimidazoles such as: carbendazim, benomyl, fuberidazole, thiabendazole or their salts; cjRAIz - 14 Morpholine derivatives such as: aldimorph, dimethomorph, dodemorph, falimorph, fenpropidin fenpropimorph, tridemorph, trimorphamid and their arylsulphonate salts such as, for example, p toluenesulphonic acid and p-dodecylphenyl-sulphonic acid; 5 Benzothiazoles such as: 2-mercaptobenzothiazole; Benzothiophene dioxides such as: 10 N-cyclohexyl-benzo[b]thiophene-S,S-dioxide carboxamide; Benzamides such as: 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide, tecloftalam; 15 Boron compounds such as: boric acid, boric ester, borax; Formaldehyde and formaldehyde-releasing compounds such as: benzyl alcohol mono-(poly)-hemiformal, n-butanol hemiformal, dazomet, ethylene 20 glycol hemiformal, hexa-hydro-S-triazine, hexamethylenetetramine, N-hydroxy methyl-N'-methylthiourea, N-methylolchloroacetamide, oxazolidine, paraformalde hyde, taurolin, tetrahydro-1,3-oxazine, N-(2-hydroxypropyl)-amine-methanol; Isothiazolinones such as: 25 N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3 -one, 4,5-dichloro-N octylisothiazolin-3-one, 5-chloro-N-octylisothiazolinone, N-octyl-isothiazolin-3-one, 4,5-trimethylene-isothiazolinone, 4,5-benzoisothiazolinone; Aldehydes such as: 30 cinnamaldehyde, formaldehyde, glutardialdehyde, B-bromocinnamaldehyde; SRA4 1 -1Z -0 Il - 15 Thiocyanates such as: thiocyanatomethylthiobenzothiazole, methylenebisthiocyanate; quaternary ammonium compounds such as: 5 benzalkonium chloride, benzyldimethyltetradecylammonium chloride, benzyl dimethyldodecylammonium chloride, dichlorobenzyl-dimethyl-alkyl-ammonium chloride, didecyldimethylammonium chloride, dioctyl-dimethyl-ammonium chloride, N-hexadecyl-trimethyl-ammonium chloride, 1-hexadecyl-pyridinium chloride; 10 Iodine derivatives such as: diiodomethyl p-tolyl sulphone, 3-iodo-2-propinyl alcohol, 4-chlorophenyl-3-iodo propargylformal, 3-bromo-2,3-diiodo-2-propenyl ethylcarbamate, 2,3,3-triiodoallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propinyl n-butyl carbamate, 3-iodo-2-propinyl n-hexylcarbamate, 3-iodo-2-propinyl-cyclohexyl 15 carbamate, 3-iodo-2-propinyl phenylcarbamate; Phenols such as: tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chloro phenol, phenoxyethanol, dichlorophen, 2-benzyl-4-chlorophenol, 5-chloro-2-(2,4-di 20 chlorophenoxy)-phenol, hexachlorophene, p-hydroxybenzoate, o-phenylphenol, m phenylphenol, p-phenylphenol and their alkali metal salts and alkaline earth metal salts; Microbicides with an activated halogen group such as: 25 bronopol, bronidox, 2-bromo-2-nitro-1,3-propanediol, 2-bromo-4'-hydroxy-aceto phenone, 1-bromo-3-chloro-4,4,5,5-tetramethyl-2-imidazoldinone, B-brom-B-nitro styrene, chloracetamid, chloramin T, 1,3-dibromo-4,4,5,5-tetrametyl-2-imidazol dinone, dichloramin T, 3,4-dichloro-(3H)-1,2-dithiol-3-one, 2,2-dibromo-3-nitril propionamide, 1,2-dibromo-2,4-dicyanobutane, halane, halazone, mucochloric acid, 30 phenyl (2-chlorocyano-vinyl) sulphone, phenyl (1,2-dichloro-2-cyanovinyl) sulphone, RAL, trichloroisocyanuric acid; -16 Pyridines such as: 1 -hydroxy-2-pyridinthione (and their Na, Fe, Mn, Zn salts), tetrachloro-4-methyl suiphonylpyridine, pyrimethanol, mepanipyrim, dipyrithion, 1 -hydroxy-4-methyl-6 5 (2,4,4-trimethylpentyl)-2( 1 H)-pyridine; Methoxyacrylates or similar such as: methyl (E)-methoximino[alpha-(o-tolyloxy)-o-tolyl]acetate, (E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)acetamide, 10 (E)-2- {2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl} -3 -methoxyacrylate, 0-Methyl 2 -[([3-methoximino-2-butyl)imino]oxy)o-tolyl]-2-methoximino acetimidate, 2- [[[[1 -(2,5-dimethylphenyl)ethylidenelaminoloxylmethyl]-.alpha.-(methoximino) N-metyl-benzeneacetamide, 15 alpha-(methoxyimino)-N-methyl-2-[[[ I -[3-(trifluoromethyl)phenyl]ethyli denelaminoloxylmethyl]-benzeneacetamide, alpha-(methoxyimino)-2-[[[[ 1-[3-(trifluoromethyl)phenyl]ethylidene]amino]oxy] methyl]-benzeneacetic acid methyl ester, alpha-(methoxymethylene)-2-[[[[ I-[3-(trifluoromethyl)phenyl]ethylidene]amino] 20 oxylmethyl]-benzeneacetic acid methyl ester, 2- [[[5-chloro-3 -(trifluoromethy1)-2-pyridinyl]oxy]methyl]-.alpha.-(methoxyimino) N-methyl-benzeneacetamide, 2 -[[[cyclopropyl[(4-ethoxyphenyl)imino]methyl]thio]methyl...alpha.

(methoxyimino)-benzeneacetic acid methyl ester, 25 alpha-(methoxyimino)-N-methyl-2-(4-methyl-5-phenyl-2,7-dioxa-3 ,6-diazaocta-3 ,5 dien- 1 -yl)-benzeneacetamide, alpha-(methoxymethylene)-2-(4-methyl-5-phenyl-2,7-dioxa3,6-diazaocta.3 ,5-dien 1 -yl)-benzeneacetic acid methyl ester, alpha-(methoxyimino)-N-methyl-2-[[[ 1-[3-(trifluoromethyl)phenyl] 30 ethoxy]imino]methyl]-benzeneacetamide, D RA

L

1 2- [[( 3 ,5-dichloro-2-pyridinyl)oxylmethyl]-.alpha.-(methoxyimino)-N-methyl benzeneacetamide, $?A1T O«~ - 17 2-[4,5-dimethyl-9-(4-morpholinyl)-2,7-dioxa-3,6-diazanona-3,5-dien- I -yl]-.alpha.

(methoxymethylene)-benzeneacetic acid methyl ester; Metal soaps such as: 5 tin naphthenate, tin octoate, tin 2-ethylhexanoate, tin oleate, tin phosphate, tin benzoate, copper naphthenate, copper octoate, copper 2-ethylhexanoate, copper oleate, copper phosphate, copper benzoate, zinc naphthenate, zinc octoate, zinc 2 ethylhexanoate, zinc oleate, zinc phosphate, zinc benzoate; 10 Metal salts such as: copper hydroxycarbonate, sodium dichromate, potassium dichromate, potassium chromate, copper sulphate, copper chloride, copper borate, zinc fluorosilicate, copper fluorosilicate; 15 Oxides such as: Tributyltin oxide, Cu2O, CuO, ZnO; Dithiocarbamates such as: cufraneb, ferban, potassium N-hydroxymethyl-N'-methyl-dithiobarbamate, sodium 20 dimethyldithiocarbamate, potassium dimethyldithiocarbamate, macozeb, maneb, metam, metiram, thiram, zineb, ziram; Nitriles such as: 2,4,5,6-tetrachloroisophthalonitrile, disodium cyano-dithioimidocarbamate; 25 Quinolines such as: 8-hydroxyquinoline and their copper salts; 4U

DO

- 18 other fungicides and bactericides such as: 5-hydroxy-2(5H)-furanone, 4,5-benzodithiazolinone, 4,5-trimethylenedithiazolinone, N-(2-p-chlorobenzoylethyl)-hexaminium chloride, 2-oxo-2-(4-hydroxy-phenyl)aceto hydroxycinnamoyl chloride, tris-N-(cyclohexyldiazeniumdioxy)-aluminium, N 5 (cyclo-hexyldiazeniumdioxy)-tributyltin or its potassium salts, bis-N-(cyclohexyl diazeniumdioxy)-copper; Ag, Zn or Cu-containing zeolites alone or incorporated into polymeric materials. 10 Very especially preferred are mixtures with azaconazole, bromuconazole, cyproconazole, dichlobutrazol, diniconazole, hexa conazole, metaconazole, penconazole, propiconazole, tebuconazole, dichlofluanid, tolylfluanid, fluorfolpet, methfuroxam, carboxin, benzo[b]thiophene S,S-dioxide N cyclohexylcarboxamide, fenpiclonil, 4-(2,2-difluoro-1,3-benzodioxol-4-yl)-1H 15 pyrrol-3-carbonitrile, butenafine, imazalil, N-methyl-isothiazolin-3-one, 5-chloro-N methylisothiazolin-3 -one, N-octylisothiazolin-3-one, dichloro-N-octyliso thiazolinone, mercaptobenthiazole, thiocyanatomethylthiobenzothiazole, benzoiso thiazolinone, N-(2-hydroxypropyl)-amino-methanol, benzyl alcohol (hemi)-formal, N-methylolchloroacetamide, N-(2-hydroxypropyl)-amine-methanol, glutaraldehyde, 20 omadin, dimethyl dicarbonate and/or 3-iodo-2-propinyl n-butylcarbamate. Apart from with the abovementioned fungicides and bactericides, mixtures with a good efficacy are, moreover, also prepared with other active compounds: 25 Insecticides / acaricides / nematicides such as: abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, alpha-cypermethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin, 30 13 RAQ/ Bacillus thuringiensis, barthrin, 4-bromo-2(4-chlorophenyl)-I-(ethoxymethyl)-5-(tri ' ~fluoromethyl)-1H-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, Beta

NT

-19 cyfluthrin, bifenthrin, bioresmethrin, bioallethrin, bromophos A, bromophos M, bufencarb, buprofezin, butathiophos, butocarboxin, butoxycarboxim, cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, quino 5 methionate, cloethocarb, chlordane, chlorethoxyfos, chlorfenvinphos, chlorfluazu rone, chlormephos, N-[(6-chloro-3-pyridinyl)-methyl]-N'-cyano-N-methyl-ethane imidamide, chlorpicrin, chlorpyrifos A, chlorpyrifos M, cis-resmethrin, clocythrin, cypophenothrin clofentezin, coumaphos, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazin, 10 decamethrin, deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron, dialiphos, diazinon, 1,2-dibenzoyl-1(1,1-dimethyl)-hydrazine, DNOC, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diflubenzuron, dimethoate, dimethyl-(phenyl)-silyl-methyl 3-phenoxybenzyl ether, dimethyl-(4-ethoxyphenyl) 15 silylmethyl-3-phenoxybenzyl ether, dimethylvinphos, dioxathion, disulfoton, eflusilanate, emamectin, empenthrin, endosulfan, EPN, esfenvalerate, ethiofencarb, ethion, ethofenprox, etrimphos, 20 fenamiphos, fenazaquin, fenbutatin oxide, fenfluthrin, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximat, fensulfothion, fenthion, fenvalerate, fipronil, fluazuron, flucycloxuron, flucythrinate, flufenoxuron, flumethrin flufenprox, fluvalinate, fonophos, formethanate, formothion, fosmethilan fosthiazate, fubfenprox, furathiocarb, 25 HCH, heptenophos, hexaflumuron, hexythiazox, hydramethylnon, hydroprene, imidacloprid, iodfenfos, iprobenfos, isazophos, isoamidophos, isofenphos, isopro carb, isoprothiolane, isoxathion, ivermectin, lama-cyhalothrin, lufenuron, 30 kadedrin - 20 lambda-cyhalothrin, lufenuron, malathion, mecarbam, mervinphos, mesulfenphos, metaldehyde, methacrifos, 5 methamidophos, methidathion, methiocarb, methomyl, metalcarb, milbemectin, monocrotophos, moxiectin, naled, NC 184, NI 125, nicotin, nitenpyram, 10 omethoate, oxamyl, oxydemethon M, oxydeprofos, parathion A, parathion M, penfluron, permethrin, 2-(4-phenoxyphenoxy)-ethyl ethylcarbamate, phenthoate, phorate, phosalon, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A, prallethrin, profenophos, promecarb, propa 15 phos, propoxur, prothiophos, prothoate, pymetrozin, pyrachlophos, pyridaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen, quinalphos, 20 resmethrin, RH-7988, rotenone, salithion, sebufos, silafluofen, sulfotep, sulprofos, tau-fluvalinate, taroils, tebufenozide, tebufenpyrad, tebupirimphos, teflubenzuron, 25 tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos, tetramethrin, Tetra methacarb, thiafenox, thiapronil, thiodicarb, thiofanox, thiazophos, thiocyclam, thiomethon, thionazin, thuringiensin, tralomethrin, triarathen, triazophos, triazamate, triazuron, trichlorfon, triflumuron, trimethacarb, 30 vamidothion, XMC, xylylcarb, zetamethrin; r 0 -21 Molluscicides such as: fentin acetate, metaldehyde, methiocarb. miclosamide; Herbicides and other algicides such as 5 acetochlor, acifluorfen, aclonifen, acrolein, alachlor, alloxydim, ametryn, amido sulfuron, amitrole, ammonium sulphamate, anilofos, asulam, atrazine, aziptrotryne, azimsulfuron, 10 benazolin, benfluralin, benfuresate, bensulfuron, bensulphide, bentazone, benzofen cap, benzthiazuron, bifenox, borax, bromacil, bromobutide, bromofenoxim, bromoxynil, butachlor, butamifos, butralin, butylate, bialaphos, benzoyl-prop, bromobutide, 15 carbetamide, chlomethoxyfen, chloramben, chlorbromuron, chlorflurenol, chloridazon, chlorimuron, chlornitrofen, chloroacetic acid, chlorotoluron, chloro xuron, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinmethylin, cinoflulsuron, clethodim, clomazone, chlomeprop, clopyralid, cyanamide, cyanazine, cycloate, cycloxydim, chloroxynil, clodinafop-propargyl, cumyluron, CGA 248757, 20 clometoxyfen, cyhalofop, clopyrasuluron, cyclosulfamuron, dichlorprop, dichlorprop-P, diclofop, diethatyl, difenoxuron, difenzoquat, diflu fenican, dimefuron, dimepiperate, dimethachlor, dimethipin, dinitramine, dinoseb, dinoseb acetate, dinoterb, diphenamid, dipropetryn, diquat, dithiopyr, diduron, 25 DNOC, DSMA, 2,4-D, daimuron, dalapon, dazomet, 2,4-DB, desmedipham, des metryn, dicamba, dichlobenil, dimethamid, dithiopyr, dimethametryn, eglinazine, endothal, EPTC, esprocarb, ethalfluralin, ethidimuron, ethofumesate, ethobenzanid, ethoxyfen, ET 751, ethametsulfuron, 30 fenoxaprop, fenoxaprop-P, fenuron, flamprop, flamprop-M, flazasulfuron, fluazifop, fluazifop-P, fuenachlor, fluchloralin, flumeturon, fluorocglycofen, fluoronitrofen, 441 'Vr op" - 22 flupropanate, flurenol, flurochloridone, fluroxypyr, fomesafen, fosamine, flamprop isopropyl, flamprop-isopropyl-L, flumiclorac-pentyl, flumipropyn, flumioxzim, flurtatone, flumioxzim, 5 glyphosate, glufosinate-ammonium haloxyfop, hexazinone, imazamethabenz, isoproturon, isoxaben, isoxapyrifop, imazapyr, imazaquin, ima 10 zethapyr, ioxynil, isopropalin, imazosulfuron, KUH 911, KUH 920 lactofen, lenacil, linuron, LS830556, 15 MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, mefenacet, mefluidide, metam, metamitron, metazachlor, methabenzthiazuron, methazole, methoroptryne, methyldymron, methyl isothiocyanate, metobromuron, metoxuron, metribuzin, metsulfuron, molinate, monalide, monolinuron, MSMA, metolachlor, metosulam, 20 metobenzuron, naproanilide, napropamide, naptalam, neburon, nicosulfuron, norflurazon, sodium chlorate, 25 oxadiazon, oxyfluorfen, orbencarb, oryzalin, quinchlorac, quinmerac, propyzamide, prosulfocarb, pyrazolate, pyrazolsulfuron, pyrazoxyfen, pyributicarb, pyridate, paraquat, pebulate, pendimethalin, pentachlorophenol, pentanochlor, petro leum oils, phenmedipham, picloram, piperophos, pretilachlor, primisulfuron, prodi 30 amine, prometryn, propachlor, propanil, propaquizafob, propazine, propham, pyrithiobac, - 23 quinmerac, quinocloamine, quizalofop, quizalofop-P, rimsulfuron 5 sethoxydim, sifuron, simazine, simetryn, sulfometuron, sulfentrazone, sulcotrione, sulfosate, tar oils, TCA, tebutam, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutryn, 10 thiazafluoron, thifensulfuron, thiobencarb, thiocarbazil, tralkoxydim, tri-allate, triasulfuron, tribenuron, triclopyr, tridiphane, trietazine, trifluralin, tycor, thdiazimin, thiazopyr, triflusulfuron, vernolate. 15 The weight ratios of the active compounds in these active compound combinations can be varied within relatively large ranges. The active compound combinations preferably comprise 0.1 to 99.9%, in particular 1 20 to 75%, very especially 5 to 50%, of the active compound, the remainder up to 100% being made up by one or more of the abovementioned components in the mixtures. The microbicidal compositions or concentrates used for protection of the industrial materials comprise the active compound, or the active compound combination, in a 25 concentration of 0.01 to 95% by weight, in particular 0.1 to 60% by weight. The use concentrations of the active compounds, or active compound combinations, to be used depends on the species and the abundance of the microorganisms to be controlled and on the composition of the material to be protected. The optimal rate 30 can be determined by test series. In general, the use concentrations are in the range of 0.001 to 5% by weight, preferably 0.05 to 1.0% by weight, based on the material to be protected.

VT

-24 The active compounds or compositions according to the invention allow the microbicidal compositions available to date to be replaced advantageously by more effective ones. They have good stability and, advantageously, a broad spectrum of 5 action. The examples which follow are intended to illustrate the invention. The invention is not restricted to the examples. OA4RA 7z-, -25 Examples Example 1 N-SO IN[.S0 2 > S S 5 N 5 g (26 mmol) of the potassium salt of 1,4,2-dithiazol-3-thiol 1,1-dioxide and 7.71 g of sodium acetate are introduced into 130 ml of acetone / 26 ml of water and the mixture is cooled to 0*C. The diazonium salt solution is added dropwise to this 10 mixture and stirring is continued for 1.5 hours at 0*C. The mixture is extracted at approx. 10*C using ethyl acetate, and the extract is dried over Na 2

SO

4 and evaporated. The residue is chromatographed on silica gel (toluene/ethyl acetate = 10:1). 15 Yield 3.1 g (4 48% of theory); physical data see Table 1. Diazonium salt solution: 2.76 g (26 mmol) of 3-aminopyridine are introduced into a mixture of 7 ml of 20 concentrated HCI and 52 ml of water and diazotized at 0 0 C with a solution of 1.9 g NaNO2 in 15.8 ml of H20. Stirring is continued for one hour at 0 0 C, whereupon 3.73 g of urea and 4,68g of sodium acetone are added to the solution. 1

N

- 26 Example 9 N-SO SS 2 g (11.6 mmol) of 3-chloro-1,4,2-dithiazole 1,1-dioxide are introduced into 5 ml of 5 DMF, and a solution of 1.38 g (12.5 mmol) and 1.26 g (12.5 mmol) of triethylamine in 5 ml of DMF are added dropwise at 10*C. Stirring is continued for 24 hours at room temperature, the mixture is poured into 50 ml of ice-water, and the crystals which have precipitated are filtered off with suction, washed with a small amount of water and dried in vacuo at 40'C. 10 Yield: 2.4 g (A 84% of theory); physical data, see Table 1. The compounds given by way of Example shown in Table 1 are obtained analogously to Example I and Example 9 and the general description. N 1T - 27 Table 1 N \Is Pyr-S H2)nS (), Ex. No. Pyr n physical constants 1 H NMR(DMSO-d6) 8=4.90 (2H, s), 7.64 (1H,m); 8.25 (1H,m); 8.81 (1H, m); 8.89 N (I1H, m). 2 2 1 H NMR(CDCl 3 ) 8=3.42 (2H, m); 3.61 (2H, m); 7.41 (1H, m); 7.93 (1H, m); 8.7 N 8.8 (2H, m). 3 1 m.p. = 141 C N CI 4 2 1 H NMR(CDCl 3 ) 5=3.42 (2H, m); 3.49 (2H, m); 7.35 (1H, m); 8.05 (1H, m); 8.55 N C1 (IH, m) 5 1 m.p.= 144C

H

3 CO N 6 2 1H NMR(CDC 3 ) 5-3.39 (2H, m); 3.51 HCO N '(2H, m); 3.98 (3H, s); 6.83 (H, d); 7.72 (1H, dd); 8.29 (1H, d) 7 1 m.p. = 213'C 8 2 -28 Table 1 (continued) Ex. No. Pyr n physical constants 9 1 m.p.= 116*C N 10 2 11N 12 N 2 13 1 m.p. =157'C

CH

3 N S N N CH 14 N.. 2 m.p. =16 0 'C Hc, N S N N N CH, Example for the synthesis of compounds of the general formula (IV)

N-SO

2 5 CI 4.5 g (24.5 mmol) of 1,4,2-dithiazole-3-methylthio 1,1-dioxide are added in the course of 10 minutes to 17 g (122 mmol) of SO 2 Cl2. The mixture is heated to 40*C jRA4/ and stirred at this temperature for 24 hours. After the excess SO 2 Cl2 has been - 29 evaporated in vacuo, the mixture is stirred with diethyl ether, filtered with suction and dried in vacuo. Yield: (3.3 g ^ 78% of theory) 5 IH NMR (CDCl 3 ) 5 = 4.67 ppm.

-30 Use Example A To demonstrate the efficacy against fungi, the minimum inhibitory concentrations (MICs) of compositions according to the invention were determined: 5 Active compounds according to the invention are added at concentrations of 0.1 mg/ I to 5000 mg/l to an agar made with malt extract. After the agar has solidified, it is contaminated with pure-bred cultures of the test organisms given in Table 2. The cultures are stored for 2 weeks at 28 0 C and a relative atmospheric humidity of 60 to 10 70%, and the MIC is then determined. MIC is the lowest concentration of active compound at which no growth whatsoever by the microbial species used takes place; it is shown in Table 2 below. Table 2 15 Minimum inhibitory concentrations (ppm) of compounds of the formula (I) according to the invention Example No. 1 2 3 5 7 13 Penicillium 20 200 <40 <40 <40 20 brevicaule Chaetomium globo- 20 200 <40 <40 <40 10 sum Aspergillus niger 20 400 100 <40 <40 100 RA4" -31 Use Example B Phytophthora test (tomato) / protective 5 Solvent: 47 parts by weight of acetone Emulsifier: 3 parts by weight of alkyl-aryl polyglycol ether To prepare a suitable preparation of active compound, I part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the 10 concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the preparation of active compound at the specified rate of application. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Phytophthora 15 infestans. The plants are then placed in an incubation cabinet at approx. 20*C and a relative atmospheric humidity of 100%. The test is evaluated 3 days after inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no infection 20 is observed. At an application rate of 100 g/ha, an efficacy of 82% is achieved with compound I according to the invention.

T

- 32 Use Example C Venturia test (apple) / protective 5 Solvent: 47 parts by weight of acetone Emulsifier: 3 parts by weight of alkyl-aryl polyglycol ether To prepare a suitable preparation of active compound, I part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the 10 concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the preparation of active compound at the specified rate of application. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the apple scab 15 pathogen Venturia inaequalis and then remain in an incubation cabinet for 1 day at approx. 20*C and a relative atmospheric humidity of 100%. The plants are then placed in the greenhouse at approx. 21*C and a relative atmospheric humidity of approx. 90%. 20 The test is evaluated 12 days after inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no infection is observed. 25 At an application rate of 100 g/ha, an efficacy of 80% is achieved with compound 1 according to the invention. C44

Claims (9)

1. 2. Compounds of the formula (I) according to Claim 1, in which Pyr is optionally mono- to pentasubstituted by halogen, alkyl having I to 10 carbon atoms, halogenoalkyl having I to 8 carbon atoms and I to 8 identical or different halogen atoms, alkoxy having I to 10 carbon atoms, halogenoalkoxy A41 having I to 8 carbon atoms and I to 8 identical or different halogen atoms, 4i - 34 alkylthio having 1 to 10 carbon atoms, halogenoalkylthio having 1 to 8 carbon atoms and 1 to 8 identical or different halogen atoms, amino, monoalkylamino having straight-chain or branched alkyl radicals having I to 6 carbon atoms, dialkylamino having identical or different straight-chain or 5 branched alkyl radicals, each of which has 1 to 6 carbon atoms, cycloalkyl having 1 to 6 carbon atoms, methylenedioxy, difluoromethylenedioxy, chiorofluoromethylenedioxy, dichloromethylenedioxy, nitro, cyano or the radical H 3 C N S- N 10 CH 3
2. 3. Compounds of the formula (I) according to Claim 1, in which Pyr is unsubstituted or mono- to tetrasubstituted, preferably mono- to disubstituted, by fluorine, chlorine, bromine, alkyl having 1 to 8 carbon atoms, preferably 15 methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, halogenoalkyl having 1 to 6 carbon atoms and 1 to 6 fluorine and/or chlorine atoms, such as preferably trifluoromethyl, trifluoroethyl, difluorochloromethyl, alkoxy having 1 to 8 carbon atoms, preferably methoxy, ethoxy, u- or i-propoxy, n-, i-, s- or t-butoxy, halogenoalkoxy having I to 6 carbon atoms and 1 to 6 fluorine 20 and/or chlorine atoms such as, preferably, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, alkylthio having 1 to 8 carbon atoms, halogenoalkylthio having 1 to 6 carbon atoms and 1 to 6 fluorine and/or chlorine atoms, amino, monoalkylamino having alkyl radicals of 1 to 4 carbon atoms, dialkylamino having identical or different alkyl radicals, each of which 25 has 1 to 4 carbon atoms, cycloalkyl having 1 to 6 carbon atoms, methylenedioxy, difluoromethylenedioxy, chlorofluoromethylenedioxy, dichloromethylenedioxy, nitro, cyano or sRAc, 77 0& H 3 CNTS CH 3 and n represents 1 or 2. 5
3. 4. Compounds of the formula (I) according to Claim 1, in which Pyr represents unsubstituted and substituted groups of the formula rL"foYorY 10
4. 5. Compositions characterized in that they comprise at least one compound of the formula (I) according to Claim 1 in combination with one or more suitable extenders and/or surfactants.
5. 6. Method of controlling pests, characterized in that compounds of the formula 15 (I) according to Claim I are allowed to act on pests and/or their environment.
6. 7. Use of compounds of the formula (I) or compositions according to Claims I to 5 for controlling pests. 20
7. 8. Process for the preparation of pesticides, characterized in that compounds of the formula (I) according to Claims I to 4 are mixed with extenders and/or surfactants.
8. 9. Process for the preparation of compounds of the formula (I) as defined in 25 Claim 1, characterized in that the salts of the general formula (II) : A . Al ,S2 N _ | (CH2)(II) , in which 5 n represents I or 2, ME represents an alkali metal ion or alkaline earth metal ion, in particular Na+, K+, 10 are reacted with diazonium salts of the general formula (III) Pyr-N=NEDA0HI in which 15 Pyr has the meaning given in Claim 1 and AO represents the anion of a mineral acid, in aqueous/alkaline solution, if appropriate in the presence of a catalyst. 20
9. 10. Compounds of the formula (IV) ,SO 2 2)n (IV), Cl S 25 in which n represents I. <fRA4Z - 37 11. Process for the preparation of compounds of the formula (I), characterized in that compounds of the formula (IV) ,SO2 N 5 (CH 2 )n (IV) 5 CI S in which n represents 1 or 2, 10 are reacted with thio compounds of the formula (V) Pyr-SH (V), 15 in which Pyr has the meaning given in Claim 1, if appropriate in the presence of bases or diluents.