N-sulfonyliminodithio compounds useful for in plant and material protection

N-sulfonyliminodithio compounds have the formula (I), in which R.sup.1 and R.sup.2 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. ##STR1##

The invention relates to new N-sulphonyliminodithio compounds, processes 
for their preparation, and use in plant and material protection. 
N-sulphonyliminodialkylthio compounds of similar structure which are 
biologically inactive have already been described (R. Gompper, H. Haigele; 
Chem. Ber. 99, 2885 (1966). 
Structurally similar N-arylsulphonyliminodithio compounds are likewise 
known, a biological action is not described (M. Hans, H. Dehne, R. 
Hartwig; Z. Chem. 26, 204 (1986). 
Further N-arylsulphonyliminothiocarboxylic acid diesters are described as 
herbicide safeners (EP 112 289). 
Surprisingly, it has now been found that the new N-sulphonyliminodithio 
compounds of the general formula (I) 
##STR2## 
in which R.sup.1 and R.sup.2 represent optionally substituted alkyl, 
alkenyl or alkinyl, and 
Ar represents optionally substituted aryl are outstandingly suitable for 
the protection of plants and materials. Additionally, new processes for 
the preparation of N-sulphonyliminodithio compounds of the formula (I) 
have been found. 
Formula (I) provides a general definition of the new N-sulphonyliminodithio 
compounds according to the invention. Preferred compounds of the formula 
(I) are those in which 
R.sup.1 and R.sup.2 independently of one another represent straight-chain 
or branched alkyl having 1 is 10 carbon atoms, straight-chain or branched 
alkenyl having 2 to 10 carbon atoms or straight-chain or branched alkinyl 
having 2 to 10 carbon atoms, which in each case are optionally mono- to 
polysubstituted identically or differently by halogen, alkoxy having 1 to 
6 carbon atoms, halogenoalkoxy having 1 to 6 carbon atoms and 1 to 9 
identical or different halogen atoms, alkylthio having 1 to 6 carbon 
atoms, halogenoalkylthio having 1 to 6 carbon atoms and 1 to 9 identical 
or different halogen atoms, acyl having 1 to 6 carbon atoms, acyloxy 
having 1 to 6 carbon atoms, (alkoxy)-carbonyl having 1 to 6 carbon atoms, 
amino which is optionally identically or differently substituted by alkyl 
or aryl, optionally in each case substituted phenoxy, aryl, pyridyl or 
pyridyloxy, nitro or cyano, and 
Ar represents aryl, 
which is optionally mono- to pentasubstituted by halogen, alkyl having 1 to 
10 carbon atoms, halogenoalkyl having 1 to 8 carbon atoms and 1 to 8 
identical or different halogen atoms, alkoxy having 1 to 10 carbon atoms, 
halogenoalkoxy having 1 to 8 carbon atoms and 1 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 halogen atoms, amino, monoalkylamino with straight-chain or 
branched alkyl radicals having 1 to 6 carbon atoms, dialkylamino with 
identical or different, straight-chain or branched alkyl radicals each 
having 1 to 6 carbon atoms, cycloalkyl having 1 to 6 carbon atoms, 
methylenedioxy, difluoromethylenedioxy, chlorofluoromethylenedioxy, 
dichloromethylenedioxy, nitro or cyano. 
Particularly preferred compounds of the formula (I) are those in which 
R.sup.1 and R.sup.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 alkinyl 
having 2 to 8 carbon atoms, which in each case are optionally mono- to 
tetrasubstituted identically or differently by fluorine, chlorine, alkoxy 
having 1 to 5 carbon atoms, halogenoalkoxy having 1 to 5 carbon atoms and 
1 to 5 fluorine and/or chlorine atoms, alylthio having 1 to 5 carbon 
atoms, halogenoalkylthio having 1 to 5 carbon atoms and 1 to 5 fluorine 
and/or chlorine atoms, acyl having 1 to 5 carbon atoms, acyloxy having 1 
to 5 carbon atoms, alkoxycarbonyl having 1 to 5 carbon atoms, amino which 
is optionally identically or differently substituted by alkyl having 1 to 
4 carbon atoms and/or phenyl, optionally in each case 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, halogenoalkyl having 
1 to 6 carbon atoms and 1 to 6 fluorine and/or chlorine atoms, alkoxy 
having 1 to 8 carbon atoms, halogenoalkoxy having 1 to 6 carbon atoms and 
1 to 6 fluorine and/or chlorine atoms, 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 with alkyl radicals of 1 to 4 
carbon atoms, dialkylamino with identical or different alkyl radicals in 
each case having 1 to 4 carbon atoms, cycloalkyl having 1 to 6 carbon 
atoms, methylenedioxy, difluoromethylenedioxy, chlorofluoromethylenedioxy, 
dichloromethylenedioxy, nitro or cyano. 
Very particularly preferably, R.sup.1 and R.sup.2 represent methyl, ethyl, 
n- and i-propyl. n-, s-, i- and t-butyl, allyl and propargyl, which in 
each case are optionally substituted and by fluorine and/or chlorine, 
methoxy or methylthio. 
It has been found that the N-sulphonyliminodithio compounds (I) are 
obtained when sulphonamides of the general formula (II) 
EQU R.sup.1 SO.sub.2 NH.sub.2 (II) 
where R.sup.1 has the abovementioned meaning, are reacted within the 
presence of a base CS.sub.2 and the resulting salt of the formula (III) 
##STR3## 
where R.sup.1 has the abovementioned meaning and A.sup..sym. represents a 
cation, such as, in particular, alkali metal, alkaline earth metal or 
trialkylammonium ion, is first made to react with a compound of the 
general formula (IV) 
EQU R.sup.2 X (IV) 
where R.sup.2 has the meaning indicated above and X represents a leaving 
group, preferably chlorine, bromine, mesyl, tosyl, and the resulting salt 
of the formula (V), 
##STR4## 
where R.sup.1, R.sup.2 and A.sup..sym. have the meanings indicated above, 
is reacted, if appropriate in the presence of catalysts, with diazonium 
salt solutions from anilines of the formula (VI) 
EQU H.sub.2 N-Ar (VI) 
where Ar has the abovementioned meaning. 
In the reaction sequence, the intermediates can either be isolated at any 
stage or the sequence can be carried out in a one-pot process without 
purification. 
The alkylation step with (IV) and the reaction with the diazonium salt can 
also be exchanged in the synthesis sequence. 
Additionally, the compounds of the general formula (I) are also obtained 
when compounds of the formula (VII), 
##STR5## 
in which R.sup.1 and Ar have the abovementioned meaning, are reacted, 
optionally in the presence of a base, with alkylating agents of the 
general formula (IV). 
In the preparation of the salts (III) from (II) using CS.sub.2 in the 
presence of a base, the reaction can be carried out in various solvents 
depending on the base employed. The reaction is preferably carried out 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. 
The bases used can be all customary bases. These preferably include 
tert-amines such as triethylamine and pyridine; alkali metal hydroxides 
such as sodium and potassium hydroxide; alkali metal carbonates and 
haydrogencarbonates such as potassium carbonate and sodium 
hydrogencarbonate; alkali metal and alkaline earth metal hydrides such as 
sodium hydride and calcium hydride; alkali metal alkoxides such as sodium 
ethoxide, potassium ethoxide, potassium methoxide, sodium ethoxide. 
In general, 2 to 3 equivalents of base are employed, but larger excesses 
are also possible. The reaction temperatures for this reaction step can be 
varied over a wide range. In general, the reaction is carried out between 
-30.degree. C. and +160.degree. C., preferably between -10.degree. C. and 
50.degree. C. The reaction can be carried out both under atmospheric 
pressure, and under pressure in an autoclave. 
For the reaction of the salt (III) with (IV) to give (V), the solvent can 
be changed. In this case, the solvents already mentioned above are 
possible for the sub-step. Preferably, however, the reaction is 
additionally carried out in the same solvent without isolation of the 
intermediates. 
The temperatures of this sub-step can be varied within a relatively wide 
range. In general, the reaction is carried out between -30.degree. C. and 
+100.degree. C., preferably between -10.degree. C. and 50.degree. C. 
For the next sub-step, which consists in the reaction of (V) with diazonium 
salts, the solvent can likewise be changed, where, however, here too the 
already mentioned solvents can be employed. Preferably, V is not isolated, 
but the reaction is additionally carried out in the same solvent. 
Preferably, a base and optionally a catalyst and then the diazonium salt 
solution are added to the solution. The bases used can be the bases 
already mentioned for the first sub-step, preferably alkali metal 
hydroxides such as, for example, potassium hydroxide or sodium hydroxide 
are employed. The catalysts employed can be all catalysts which promotes 
the replacement of the diazonium function by sulphur-containing radicals. 
Preferably, Cu(I) salts or copper powder are added. The temperature during 
the addition of the diazonium salt solution can be varied over a wide 
range. In general, the reaction is carried out between -30.degree. C. and 
60.degree. C., preferably between -20.degree. C. and 40.degree. C. 
The preparation of the diazonium salt solution from anilines is carried out 
according to literature methods. 
The active compounds according to the invention have a strong microbicidal 
action and can be employed for the control of undesired micro-organisms, 
such as fungi and bacteria, in plant protection and in material 
protection. 
Materials in the present connection are to be understood as meaning 
non-living materials which have been prepared for use in industry. For 
example, lacuna! can be industrial materials which are to be protected 
from microbial change or destruction by active compounds according to the 
invention, adhesives, sizes, paper and card, textiles, leather, wood, 
paints and synthetic articles, cooling lubricants and other materials 
which can be attacked or decomposed by micro-organisms. In the context of 
the materials to be protected, parts of production plants, for example 
cooling water circulations which can be adversely affected by 
multiplication of micro-organisms may also be mentioned. In the context of 
the present invention, industrial materials which may be mentioned are 
preferably adhesives, sizes, papers and cards, leather, wood, paints, 
cooling lubricants and heat-transfer fluids. 
Micro-organisms which may be mentioned which can cause degradation or 
alteration of the industrial materials are, for example, bacteria, fungi, 
yeasts, algae and slime organisms. Preferably, the active compounds or 
compositions according to the invention act against bacteria, fungi, in 
particular mould fungi, and against slime organisms and algae. 
Micro-organisms of the following genera, for example, 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 plant protection are employed for controlling 
Plasmodiophoro-mycetes, Oomycetes, Chytridiomycetes, Zygomycetes, 
Ascomycetes, Basidiomycetes and Deuteromycetes. 
Some causative organisms of fungal diseases which come 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 (conidia form: Drechslera, syn: Helminthosporium); 
Cochliobolus species, such as, for example, Cochliobolus sativus (conidia 
form: Drechslera, syn: 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; 
Altemaria species, such as, for example, Altemaria brassicae and 
Pseudocercosporella species, such as, for example, Pseudocercosporella 
herpotrichoides. 
The good toleration, by plants, of the active compounds, at the 
concentrations required for combating plant diseases, permits treatment of 
above-ground parts of plants, of vegetative propagation stock and seeds, 
and of the soil. 
Depending on their particular 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 capsules in polymeric substances. 
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 surface-active agents, that is, emulsifying 
agents and/or dispersing agents, and/or foam-forming agents. In the case 
of the use of water as an extender, organic solvents can, for example, 
also be used as auxiliary solvents. 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 as well as their ethers and 
esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl 
ketone or cyclohexanone, strongly polar solvents, such as 
dimethylformamide and dimethyl sulphoxide, as well as 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 halogenated hydrocarbons as well 
as butane, propane, nitrogen and carbon dioxide; suitable solid carriers 
are: for example ground natural minerals, such as kaolins, clays, talc, 
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, as well as synthetic granules of inorganic and organic 
meals, and granules of organic material such as sawdust, coconut shells, 
maize cobs and tobacco stalks; suitable emulsifying and/or foam forming 
agents are: for example non-ionic and anionic emulsifiers, such as 
polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, 
for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, 
arylsulphonates as well as albumen hydrolysis products; suitable 
dispersants are: for example 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 mineral and vegetable oils. 
It is possible to use colourants 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. 
The activity and the spectrum of action of the active compounds of the 
formula (I) or the compositions, precursors or, very generally, 
formulations which can be prepared therefrom can be increased if other 
antimicrobially active compounds, fungicides, bactericides, herbicides, 
insecticides or other active compounds for increasing the spectrum of 
action or achieving particular effects such as, for example, the 
additional protection from insects, are optionally added. These mixtures 
may have a wider spectrum of action than the compounds according to the 
invention. 
In many cases, synergistic effects are obtained here, i.e. the activity of 
the mixture is greater than the activity of the individual components. 
Particularly favourable mixing components are, for example, the following 
compounds: 
Triazoles such as: 
Amitrole, azocyclotin, BAS 480F, bitertanol, difenoconazole, fenbuconazole, 
fenchlorazole, fenethanil, fluquinconazole, flusilazole, flutriafol, 
imibenconazole, isozofos, myclobutanil, metconazole, epoxyconazole, 
paclobutrazol, penconazole, propioconazole, 
(.+-.)-cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol, 
tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole, 
triticonazole, uniconazole, and their metal salts and acid adducts. 
Imidazoles such as: 
Imazalil, pefurazoate, prochloraz, triflumizole, 
2-(1-tert-butyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol, 
thiazolecarboxanilides such as 
2',6'-dibromo-2-methyl-4-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole- 
5-carboxanilide, 1-imidazolyl-1-(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-methoxyacrylat 
e, 
methyl(E-2-2-6-(2-thioamidophenoxy)pyrimidin-4-yloxy!phenyl!-3-methoxyac 
rylate, 
methyl(E)-2-2-6-(2-fluorophenoxy)pyrimidin-4-yloxy!phenyl!-3-methoxyacry 
late, 
methyl(E-2-2-6-(2,6-difluorophenoxy)pyrimidin-4-yloxy!phenyl!-3-methoxya 
crylate, 
methyl(E-2-2-3-(pyrimidin-2-yloxy)phenoxy!phenyl!-3-methoxyacrylate, 
methyl(E)-2-2-3-(5-methylpyrimidin-2-yloxy)-phenoxy!phenyl!-3-methoxyacr 
ylate, 
methyl(E)-2-2-3-(phenyl-sulphonyloxy)phenoxy!phenyl!-3-methoxyacrylate, 
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)pyrrol-1-yl!-3-methoxyacrylate, 
methyl(E)-2-2-(3-methoxyphenoxy)phenyl!-3-methoxyacrylate, 
methyl(E)-2-2-(2-phenylethen-1-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)-phenoxy)phenyl)-3-methoxyacr 
ylate, 
methyl(E)-2-(2-3-(alpha-hydroxybenzyl)-phenoxy!phenyl)-3-methoxyacrylate, 
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-methoxyacrylate, 
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-methoxyacry 
late, 
methyl(E)-2-2-(5-bromopyridin-2-yloxymethyl)phenyl!-3-methoxyacrylatemeth 
yl(E)-2-2-(3-(3-iodopyridin-2-yloxy)phenoxy)phenyl!-3-methoxyacrylate, 
methyl(E)-2-2-6-(2-chloropyridin-3-yloxy)pyrimidin-4-yloxy!phenyl!-3-met 
hoxyacrylate, 
(E),(E)methyl-2-2-(5,6-dimethylpyrazin-2-ylmethyloximinomethyl)-phenyl 
!-3-methoxyacrylate, 
(E)-methyl-2-{2-6-(6-methylpyridin-2-yloxy)pyrimidin-4-yloxy!phenyl 
}-3-methoxyacrylate, 
(E),(E)methyl-2-{2-(3-methoxyphenyl)methyloximinomethyl!phenyl}-3-methoxya 
crylate, 
(E)-methyl-2-{2-(6-(2-azidophenoxy)-pyrimidin-4-yloxy!phenyl}3-methoxyacry 
late, 
(E),(E)methyl-2-{2-6-phenylpyrimidin-4-yl)-methyloximinomethyl!phenyl}-3- 
methoxyacrylate, 
(E),(E)methyl-2-{2-(4-chlorophenyl)-methyloximinomethyl!phenyl}-3-methoxy 
acrylate, 
(E)methyl-2-{2-6-(2-n-propylphenoxy)-1,3,5-triazin-4-yloxy!phenyl}-3-meth 
oxyacrylate, 
(E),(E)methyl-2-{2-(3-nitrophenyl)methyloximinomethyl!phenyl}-3-methoxyac 
rylate; 
Succinate dehydrogenase inhibitors such as: 
Fenfuram, furcarbanil, cyclafluramid, furmecyclox, seedvax, metsulfovax, 
pyrocarbolid, 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-ine); 
sulphenamides such as dichlofluanid, tolylfluanid, folpet, fluorfolpet; 
captan, captofol; 
benzimidazoles such as carbendazim, benomyl, furathiocarb, fuberidazole, 
thiophonatemethyl, thiabendazole or their salts; 
morpholine derivatives such as tridemorph, fenpropimorph, falimorph, 
dimethomorph, dodemorph, aldimorph, fenpropidin and their arylsulphonyl 
salts, such as, for example, p-toluenesulphonic acid and 
p-dodecylphenyl-sulphonic acid; 
dithiocarbamates, cufraneb, ferbam, mancopper, mancozeb, maneb, metam, 
metiram, thiram zeneb, ziram; 
benzothioazoles such as 2-mercaptobenzothiazole; 
benzamides such as 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide; 
boron compounds such as boric acid, boric acid esters, borax; 
formaldehyde and formaldehyde-cleaving compounds such as benzyl alcohol 
mono-(poly)-hemiformal, oxazolidines, hexa-hydro-S-triazines, 
N-methylolchloroacetamide, paraformadehyde, nitropyrin, oxolinic acid, 
tecloftalam; 
tris-N-(cyclohexyldiazeniumdioxy)-aluminium, 
N-(cyclo-hexyldiazeniumdioxy)tributyltin or K salts, 
bis-N-(cyclohexyldiazeniumdioxy)-copper; 
N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 
4,5-dichloro-N-octyl-isothiazolin-3-one, N-octyl-isothiazolin-3-one, 
4,5-trimethylene-isothiazolinones, 4,5-benzisothiazolinones, 
N-methylolchloroacetamide; 
aldehydes such as cinnamaldehyde, formaldehyde, glutaraldehyde, 
.beta.-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-tolylsulphone, 3-iodo-2-propinyl 
alcohol, 4-chlorophenyl-3-iodopropargyl formal, 
3-bromo-2,3-diiodo-2-propenylethyl carbamate, 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-hexyl carbamate, 
3-iodo-2-propinyl-cyclohexylcarbamate, 3-iodo-2-propinyl-phenyl 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 metal and alkaline earth metal 
salts; 
microbicides having an activated halogen group, such as chloroacetamide, 
bronopol, bronidox, tectamers such as 2-bromo-2-nitro-1,3-propanediol, 
2-bromo-4'-hydroxyacetophenone, 2,2-dibromo-3-nitrile-propionamide, 
1,2-dibromo-2,4-dicyanobutane, .beta.-bromo-.beta.-nitrostyrene; 
pyridines such as 1-hydroxy-2-pyridinethione (and their Na, Fe, Mn, Zn 
salts), tetrachloro-4-methylsulphonylpyridine, pyrimethanol, mepanipyrim, 
dipyrithione, 1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2(1H)-pyridine; 
metal soaps such as tin, copper or zinc naphtenate, octoate, 
2-ethylhexanoate, oleate, phosphate or benzoate; 
metal salts such as copper hydroxycarbonate, sodium dichromate, potassium 
dichromate, potassium chromate, copper sulphate, copper chloride, copper 
borate, zinc fluorosilicate, copper fluorosilicate; 
oxides such as tributyltin oxide, Cu.sub.2 O, CuO, ZnO; 
dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates, 
tetramethylthiuram disulphide, potassium N-methyl-dithiocarbamate; 
nitriles such as 2,4,5,6-tetrachloroisophthalodinitrile, disodium 
cyano-dithioimidocarbamate; 
quinolines such as 8-hydroxyquinoline and their Cu salts; 
mucochloric acid, 5-hydroxy-2(5H)-furanone; 
4,5-dichlorodithiazolinone,4,5-benzodithiazolinone,4,5-trimethylenedithiazo 
linone,4,5-dichloro-(3H)-1,2-dithiol-3-one, 
3,5-dimethyl-tetrahydro-1,3,5-thiadiazine-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 sulphone, 
phenyl 1,2-dichloro-2-cyano-vinyl sulphone, 
Ag, Zn or Cu-containing zeolites on their own or included in polymeric 
active compounds. 
Very particularly preferred mixtures are those with azaconazole, 
bromuconazole, cyproconazole, dichlobutrazole, diniconazole, hexaconazole, 
metaconazole, penconazole, propioconazole, tebuconazole, methyl 
(E)-methoximino.alpha.-(o-tolyloxy)-o-tolyl)!acetate, methyl 
(E)-2-{2-6-(2-cyanophenoxy)-pyrimidin-4-yl-oxy!phenyl}-3-methoxyacrylate, 
methfuroxam, carboxin, fenpiclonil, 
4-(2,2-difluoro-1,3-benzodioxol-4-yl)-1H-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, benzylalcohol 
(hemi)-formal, glutaraldehyde, omadine, dimethyl dicarbonate and/or 
3-iodo-2-propinyl-n-butyl carbamate. 
In addition, highly effective mixtures are also prepared using the 
following active compounds: 
Fungicides: 
Acypetacs, 2-aminobutane, ampropylfos, anilazine, benalaxyl, bupirimate, 
quinomethionate, chloroneb, chlozolinate, cymoxanil, dazomet, diclomezine, 
dichloram, diethofencarb, dimethirimol, diocab, dithianon, dodine, 
drazoxolon, edifenphos, ethirimol, etridiazole, fenarimol, fenitropan, 
fentin acetate, fentin hydroxide, ferimzone, fluazinam, fluromide, 
flusulphamide, flutriafol, fosetyl, fthalide, furalaxyl, guazatine, 
hymexazol, iprobenfos, iprodione, isoprothiolane, metalaxyl, 
methasulfocarb, nitrothalisopropyl, nuarimol, ofurace, oxadiyl, 
perflurazoate, pencycuron, phosdiphen, pimaricin, piperalin, procymidone, 
propamocarb, propineb, pyrazophos, pyrifenox, pyroquilon, quintozene, tar 
oils, tecnazene, thicyofen, thiophanate-methyl, tolclofos-methyl, 
triazoxide, trichlamide, tricyclazole, triforine, vinclozolin. 
Insecticides: 
Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, 
.alpha.-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, .alpha.-2-(1-methylpropyl)-phenyl 
methylcarbamate, butocarboxim, butoxycarboxim, carbaryl, carbofuran, 
carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb, 
promecarb, propoxur and thiodicarb; 
organosilicon compounds, preferably 
dimethyl(phenyl)silyl-methyl-3-phenoxybenzyl ethers such as 
dimethyl-(4-ethoxyphenyl)-silylmethyl-3-phenoxybenzyl ether or 
(dimethylphenyl)-silyl-methyl-2-phenoxy-6-pyridylmethyl ethers, such as, 
for example, 
dimethyl-(9-ethoxy-phenyl)-silylmethyl-2-phenoxy-6-pyridylmethyl ether or 
(phenyl)-3-(3-phenoxyphenyl)-propyl! (dimethyl)-silanes such as, for 
example, 
(4-ethoxyphenyl)-3-(4-fluoro-3-phenoxyphenyl-propyl!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-trifluoro-methylvinyl)cyclopropane-carboxylate, 
fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, 
fluvalinate, permethrin, resmethrin and tralomethrin; 
nitroimines and nitromethylenes such as 
1-(6-chloro-3-pyridinyl)-methyl!-4,5-dihydro-N-nitro-1H-imidazol-2-amine 
(imidacloprid), N-(6-chloro-3-pyridyl)methyl-!N.sup.2 -cyano-N.sup.1 
-methylacetamide (NI-25); 
abamectin, AC 303, 630, acephate, acrinathrin, alanycarb, aldoxycarb, 
aldrin, amitraz, azamethiphos, Bacillus thuringiensis, phosmet, 
phosphamidon, phosphine, prallethrin, propaphos, propetamphos, prothoate, 
pyraclofos, pyrethrins, pyridaben, pyridafenthion, pyrifoxyfen, 
quinalphos, RH-7988, rotenone, sodium fluoride, sodium hexafluorosilicate, 
sulfotep, sulfuryl 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, Verticillium Lacanii, XMC, xylylcarb, benfuracarb, bensultap, 
bifenthrin, bioallethrin, MERbioallethrin (S)-cyclopentenyl isomer, 
bromophos, bromophos-ethyl, buprofezin, cadusafos, calcium polysulphide, 
carbophenothion, cartap, quinomethionate, chlordane, chlorfenvinphos, 
chlorfluazuron, chlormephos, chloropicrin, chlorpyrifos, cyanophos, 
beta-cyfluthrin, alpha-cypermethrin, cyophenothrin, cyromazine, dazomet, 
DDT, demeton-S-methylsulphone, diafenthiuron, dialifos, dicrotophos, 
diflubenzuron, dinoseb, deoxabenzofos, diaxacarb, disulfoton, DNOC, 
empenthrin, endosulfan, EPN, esfenvalerate, ethiofencarb, ethion, 
etofenprox, fenobucarb, fenoxycarb, fensulfothion, fipronil, 
flucycloxuron, flufenprox, flufenoxuron, fonofos, formetanate, formothion, 
fosmethilan, furathiocarb, heptachlor, hexaflumuron, hydramethylnon, 
hydrogen cyanide, hydroprene, IPSP, isazofos, isofenphos, isoprothiolane, 
isoxathion, iodofenphos, kadethrin, lindane, malathion, mecarbam, 
mephosfolan, mercurous, chloride, metam, Metarthizium, aniospliae, 
methacrifos, methamidophos, methidathion, methiocarb, methoprene, 
methoxychlor, methyl isothiocyanate, metholcarb, mevinphos, monocrotophos, 
naled, neodiprion sertifer NPV, nicotine, omethoate, oxydemeton-methyl, 
pentachlorophenol, petroleum oils, phenothrin, phenthoate, phorate; 
Molluscicides: 
Fentin acetate, metaldehyde, methiocarb, niclosamide, thiodicarb, 
trimethacarb. 
Algicides: 
Copper sulphate, dichlorophen, endothal, fentin acetate, quinoclamine. 
Herbicides 
Acetochlor, acifluorfen, aclonifen, acrolein, alachlor, alloxydim, ametryn, 
amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam atrazine, 
aziptrotryne, benazolin, benfluralin, benfuresate, bensulfuron, 
bensulfide, bentazone, benzofencap, benzthiazuron, bifenox, bilanafos, 
borax, dichlorprop, dichlorprop-P, diclofop, diethatyl, difenoxuron, 
difenzoquat, diflufenican, dimefuron, dimepiperate, dimethachlor, 
dimethametryn, dimethipin, dimethylarsinic acid, dinitramine, dinoseb, 
dinoseb, dinoseb acetate, dinoseb, bromacil, bromobutide, bromofenoxim, 
bromoxynil, butachlor, butamifos, fuenachlor, butralin, butylate, 
carbetamide, CGA 184927, chlormethoxyfen, chloramben, chlorbromuron, 
chlorbutam, chlorfurenol, chloridazon, chlorimuron, chlomitrofen, 
chloroacetic acid, achloropicrin, chlorotoluron, chloroxuron, 
chlorprepham, chlorsulfuron, chlorthal, chlorthiamid, cinmethylin, 
cinofulsuron, clethodim, clomazone, clomeprop, clopyralid, cyanamide, 
cyanazine, dinoseb acetate, dinoterb, diphenamid, dipropetryn, diquat, 
dithiopyr, diduron, DNOC, PPX-A 788, DPX-E96361, DSMA, eglinazine, 
endothal, EPTC, esprocarb, ethalfluralin, ethidimuron, ethofumesate, 
fenoxaprop, fenoxaprop-P, fenuron, flamprop, flamprop-M, flazasulfuron, 
fluazifop, fluazifop-P, fluchloralin, flumeturon, fluorocgycofen, 
fluoronitrofen, flupropanate, flurenol, fluridone, flurochloridone, 
fluoroxypyr, cycloate, cycloxydim, 2,4-D, daimuron, dalapon, dazomet, 
2,4-DB, desmedipham, desmetryn, dicamba, dichlorbenil, isoproturon, 
isouron, isoxaben, isoxapyrifop, lactofen, lenacil, linuron, LS830556, 
MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, mefanacet, mefluidide, 
metam, metamitron, metazachlor, methabenzthiazuron, methazole, 
methoproptryne, methyldymron, methyl isothiocyanate, metobromuron, 
fomosafen, fosamine, furyloxyfen, glufosinate, glyphosate, haloxyfop, 
hexazinone, imazamethabenz, imazapyr, imazaquin, imazethapyr, ioxynil, 
isopropalin, propyzamide, prosulfocab, pyrazolynate, pyrazolsulfuron, 
pyrazoxyfen, pyributicarb, pyridate, quinclorac, quinmerac, quinocloamine, 
quizalofop, quzizalofop-P, S-23121, sethoxydim, sifuron, simazine, 
simetryn, SMY 1500, sodium chlorate, sulfometuron, tar oils, TCA, 
metolachlor, metoxuron, metribzin, metsulfuron, molinate, monalide, 
monolinuron, MSMA, naproanilide, napropamide, naptalam, neburon, 
nicosulfuron, nipyraclofen, norflurazon, orbencarb, oaryzalin, oxadiazon, 
oxyfluorfen, paraquat, pebulate, pendimethalin, pentachlorophenol, 
pentaochlor, petroleum oils, phenmedipham, picloram, piperophos, 
pretilachlor, primisulfuron, prodiamine, proglinazine, propmeton, 
prometryn, 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 compounds in these active compound 
combinations can be varied within relatively wide ranges. 
Preferably, the active compound combinations contain the active compound to 
0.1 to 99.9%, in particular to 1 to 75%, particularly preferably 5 to 50%, 
the remainder to 100% being made up by one or more of the abovementioned 
mixture components. 
The microbicidal compositions or concentrates used for the protection of 
the industrial materials contain the active compound or the active 
compound combination in any concentration of 0.01 and 95% by weight, in 
particular 0.1 to 60% by weight. 
The application concentrations of the active compounds or of the active 
compound combinations to be used depend on the nature and the occurrence 
of the micro-organisms to be combated and on the composition of the 
material to be protected. The optimum use 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 compounds or compositions according to the invention 
advantageously make it possible to replace the microbicidal compositions 
available until now by more effective and less toxic compositions. They 
show good stability and advantageously have a wide spectrum of action.