DE2051117A1 - Tri-and tetrachloroalkyl sulphones - with fungicidal, bactericidal, a and rodent - and ruminant-repellant properties - Google Patents

Abstract

Title cpds. contain a sulphone of the formula: Cl2C(X)-CHCl-SO2-R (I) (where X is H or Cl and R is is not >6C alkyl, or aryl mono- or polysubstd. by halogen, CF3, is not >4C alkyl and/or NO2). They may be prepd. by oxidation of corresponding sulphides with peracetic acid.

Description

Fungicidal, bactericidal and acaricidal agents and repellants against Nose Animals and Ruminants The present invention relates to the use of partially known trichloro and tetrachloroethyl-alkyl-sulfones or trichloro and tetrachloroethyl aryl sulfones as fungicides, bactericides and acaricides and as Deterrents against rodents and ruminants. The use of the well-known sulfones as an insecticide is already known.

It is already known that, for. B. Zinc ethylene bisdi = thiocarbamidate and N-trichloromethylmercapto-4-cyclohexene-i 2-dicarboximide fungicidal properties (see U.S. Patents 2,457,674, 2,553,770, and 2,553,771); while Tetramethylthiuram disulfide as a repellent for rodents, rabbit-like animals and ruminants are known (cf.

J. F. Welch, Proceedings Third Vertebrate Pest Conf., San Francisco, 1967, pp. 36-40). The effect of these previously known compounds at low application concentrations however, it is not always satisfactory.

It has been found that the partially known trichloro- and tetrachloroethyl-alkyl-sulfones or trichloro- and tetrachloro-ethyl-aryl-sulfones of the formula in which X stands for hydrogen or chlorine and R stands for alkyl with up to 6 carbon atoms and for aryl, whereby the latter can be substituted one or more times by halogen, trifluoromethyl, alkyl with up to 4 carbon atoms and / or nitro groups, strong fungicidal, have bactericidal and acaricidal properties and a good deterrent effect against rodents and ruminants.

Surprisingly, the inventively usable trichloro show and tetrachloroethyl-alkyl-sulfones or trichloro- and tetrachloroethyl-aryl-sulfones a higher fungicidal, bactericidal and acaricidal effect and a better deterrent effect against rodents and ruminants as previously known compounds. So are they in comparison to zinc-ethylenehisdi = thiocarbamate superior fungicidal effect against soil-dwelling, To highlight seed-borne and sprout-parasitic fungi, as well as those of o-oxydiphenyl superior bactericidal effect and that of tetramethylthiuram disulfide Deterrent against rodents and ruminants. The to be used according to the invention Fabrics are a real asset to technology.

Due to the formula (I), the products in question are general Are defined. R preferably represents a straight-chain or branched alkyl radical with 1 to 4 carbon atoms or for phenyl, which is optionally replaced by chlorine, fluorine and / or alkyl may be substituted with 1 to 3 carbon atoms.

Examples of the substances that can be used according to the invention are im called individual: 1-chloro-2,2-dichloroethyl-methyl-sulfone 1-chloro-2,2-dichloroethyl-ethyl sulfone 1-chloro-2,2-dichloroethyl-propyl-sulfone 1-chloro-2,2-dichloroethyl-isopropyl-sulfone 1-chloro-2,2-dichloroethyl-n-butyl sulfone 1-chloro-2,2-dichloroethyl tert-butyl sulfone 1-chloro-2,2-dichloroethyl-sec-butyl-sulfone 1-chloro-2,2-dichloroethyl-phenyl-sulfone 1-chloro-2,2-dichloroethyl- (4'-chlorophenyl) -sulfone 1-chloro-2,2-dichloroethyl- (4'-fluorophenyl) -sulfone 1-chloro-2, <- dichloroethyl-v4'-methylphenyl-sulfone 1-chloro-2,2-dichloroethyl- (4'-ethylphenyl) sulfone 1-chloro-2,2-dichloroethyl (2 ', 5' '- dichlorophenyl) sulphone 1-chloro-2,2-dicloroethyl (2', 5r-dibromopnenyl) sulphone 1-chloro-2,2,2-trichloroethyl-methyl-sulfone 1-chloro-2,2,2-trichloroethyl-ethyl-sulfone 1-chloro-2,2,2-trichloroethyl-propyl-sulfone 1-chloro-2,2,2-trichloroethyl-isopropyl-sulfone 1-chloro-2,2,2-trichloroethyl-n-butyl-sulfone 1-chloro-2,2,2-trichloroethyl-tert-butyl-sulfone 1-chloro-2,2,2-trichloroethyl-sec-butyl-sulfone 1-chloro-2,2,2-trichloroethyl-phenyl-sulfone 1-chloro-2,2,2-trichloroethyl- (4'-chlorophenyl) -sulfone 1-chloro-2,2,2-trichloroethyl- (4'-fluorophenyl) -sulfone 1-chloro-2,2,2-trichloroethyl- (4s-methylphenyl) -sulphone 1-chloro-2,2,2-trichloroethyl- (4'-ethylphenyl) -sulphone 1-chloro-2,2,2-trichloroethyl- (2r s5'-dichlorophenyl) -sulphone 1-chloro-2,2,2-trichloroethyl- (2 ', 5'-dibromophenyl) -sulphone 1-chloro-Z, 2,2-trichloroethyl- (4-isopropylphenyl) -sulfone Some of the present Invention to be used products, as well as their production and insecticidal properties are known from the literature, namely the 1,2,2,2-trachloroethyl-methyl-sulfone, 1,2,3,2-tetrachloroethylethyl sulfone and 1,2,2,2 ~ tetrachloroethyl phenyl sulfone (cf. Liebigs Ann. Chem. 587, 51-62 (1954)). The others which can be used according to the invention Products have not yet been described, but they are sirg according to customary methods easily accessible. So the products are obtained if you have the appropriate Trichloro and tetrachloroethyl alkyl thioethers or the trichloro and tetrachloroethyl aryl thioethers with peracids, such as peracetic acid, at temperatures between 40 and 80 ° C in a solution resp.

Diluents, e.g. B. glacial acetic acid, oxidized. The reaction products is isolated by evaporating the solvent in vacuo after stirring for several hours and the mostly oily residue in methylene chloride or another inert, organic Absorbs solvent, washed with water and, after drying, over sodium sulfate the solvent is drawn off and the crude product obtained is purified by distillation.

The active ingredients according to the invention are highly fungitoxic Effect against soil-dwelling, seed-borne and sprout-parasitic fungi, whereby the substances according to the invention are particularly used for soil treatment and for seed dressing or are suitable for sprout application. Their effect is particularly directed against burn diseases of the grain, such as wheat stone brandy and oat brandy, furthermore against helminthosporiosis of barley and oats, e.g. B. the streak disease the barley, also against seedling diseases, e.g. B. on cereals, corn, legumes or cotton caused by fungi, e.g. B. of the genera Rhizoctonia or Fusarium.

However, the active ingredients are also suitable for combating such phytopathogenic Fungi that attack parts of plants above ground.

The active compounds according to the invention can be mixed in the formulations present with other known active ingredients, such as. B. fungicides, insecticides, Acaricides, nematicides, plant nutrients and soil structure improvers.

The active ingredients can be used as such, in the form of their formulations or the application forms prepared therefrom, such as ready-to-use solutions, emulsions, Suspensions, powders, pastes and granules. The application happens in the usual way, e.g. B. by spraying, spraying, misting, dusting, scattering, Pouring, dry pickling, slurry pickling, moist pickling or wet pickling.

The fungicidal formulations generally contain an active ingredient content from 0.1 to 95 percent by weight, preferably from 0.5 to 90.

The active ingredients can be used as such, as special formulations or be used as ready-to-use preparations. Especially in the latter form the concentration of the active substance can be very different. Generally lies they are between 0.00001 and 5%.

For soil treatment, amounts of active ingredients from 1 to 500 g per soil, preferably 10 to 200 g is required.

In the treatment of seeds, amounts of active ingredient of 0.01 to 50 g per kg of seed, preferably 0.1 to 5 g, are required.

The substances according to the invention are also of interest as microbicides. Due to their superior antimicrobial effects, which affect a wide range of Microorganisms, the compounds are used for many purposes of disinfection, Preservation and antimicrobial finish suitable; also lies a good aligcidal effect.

As microorganisms, combating them is of economic importance are to be mentioned: Aspergillus niger, Penicil = lium camerunense and Paecilomyces varioti as a representative of resistant molds, as well as Trichophyton mentagrophytes as a common athlete's foot. Candida albicans and Saccharomyces spec. belong to the Yeasts, which often appear as pathogenic forms. Escherichia coli, Bacterium proteus, Pseudomonas pyocyanea and Staphylococcus aureus are among the gram-negative or gram-positive bacteria, some of them are pathogenic.

The fabrics are also suitable for preserving wood pulp, the preliminary product for paper manufacture.

The substances according to the invention also have strong acaricidal properties especially against acarids, the animals domesticated as animal ectoparasites infested. They are therefore well suited for combating animal ectoparasites from the order of the acarids.

Ticks are considered to be economically important ectoparasites of this order from the family of the Ixodidae that live in tropical, subtropical, and temperate latitudes play a big role called. Furthermore, mites from the family Sarcoptidae, such as the sheep-sucking mite (Paoroptes ovis), the rabbit sucking mite (Pooroptes cuniculi), and Members of the Dermanyseidae family, such as the red poultry mite (Dermanyssus gallinae), be fought.

Depending on the intended form of administration, the active ingredients can be used as Animal acaricides in the formulations customary in practice to be convicted, such as solutions, emulsions, suspensions, powders, pastes and granulates.

The formulations for animal acaricides generally contain between 0.1 and aew .-% active ingredient, preferably between 0.5 and 90 wt .-%. The application concentrations are made from the formulations by diluting them with water.

Depending on the form of application, they can be varied over a wide range are and are between 10 and 50,000 ppm, preferably between 100 and 10,000) ppm.

The application takes place in the usual way, for. B. by spraying, pouring , Nebulization or as a bath (dip.) The compounds according to the invention also have a deterrent effect against harmful rabbit-like animals (Lagomorpha), against rodents and against ruminants R inantia).

The use of the active ingredients according to the invention, their formulations and the application forms produced therefrom for deterring harmful rabbit-like animals Animals, rodents and ruminants are done in the usual way, e.g. B.

by treating seeds, by spraying, dusting or scattering suitable preparations of active ingredients on by rodents and / or browsing by ruminants (Game browsing) endangered plants or parts of plants through soil treatment Smoke in rooms or underground buildings, above or below ground Application of deterrent coatings and barriers as well as impregnation for rodent and / or materials endangered by ruminants, such as wood, paper, rubber and plastics.

To achieve a deterrent effect, it is used for seed treatment generally 0.01 to 5 parts by weight of active ingredient per 100 parts by weight of seed1, preferably between 0.025 and 1.

Spray mixtures or pastes to create rodent repellants and ruminant repellent coverings z. B. on endangered plants or parts of plants generally contain between 0.1 and 20% by weight of active ingredient, preferably between 0.5 and 10. Materials that are soaked with the active ingredients are said to be in the surface layer have an active ingredient concentration of about 0.1 to 5% by weight.

The following usage examples serve as an explanation: example A: Agar plate test Examination of fungitoxic efficacy and the breadth of the spectrum of activity.

Solvent: Acetone Parts by weight: a) 1000 b) 100 For preparation an appropriate preparation of active ingredient, 1 part by weight of active ingredient is taken in the specified amount of solvent.

The preparation of the active ingredient is given to potato dextrose agar, which through Heating is liquefied in such an amount that it contains the desired concentration of active ingredient comes about.

After thorough shaking for even distribution of the active ingredient the agar is poured into Petri dishes under sterile conditions. After solidification of the substrate-active substance mixture are test mushrooms from pure cultures in discs 5 mm in diameter. The Petri dishes are left for 3 days for incubation stand at 200 C for a long time.

After this time, the inhibitory effect of the active ingredient on the mycelial wax Determined in categories taking into account the untreated control. Included 0 means no Nyzel growth, neither on the treated substrate nor on the Inoculum; - means mycelium growth only on the inoculum, no overgrowth on that treated substrate; and + means mycelial growth from inoculum to treated Substrate, similar to the overgrowth on the untreated substrate of the control.

Active ingredients, active ingredient concentrations, test mushrooms and the inhibitory effects achieved are shown in the following table: Table Agar plate test Active ingredient active ingredient conc. in the Corticium Scerotinia Verticillium Thielaviopsis Phytophtora Fusarium Fusarium Fusarium Substrate rolfsii sclerotiorum alboastrum basicola cactorum culmorum oxysporum solani in mg / l f.pisi untreated - + + + + + + + + S. # CH2-NH-CS # # a) 10 + + + + + + + # Zn b) 100 + + + 0 + + + # # CH2-NH-CS # S. (known) Cl3C-C-CH-SO2-C3H7-n b) 100 0 0 0 0 0 0 0 0 # Cl Cl2CH-CH-SO2- # b) 100 0 0 0 0 0 0 0 0 # Cl Continuation of table Agar plate test Active ingredient active ingredient conc. in the Corticium Scerotinia Verticillium Thielaviopsis Phytophtora Fusarium Fusarium Fusarium Substrate rolfsii sclerotiorum alboastrum basicola cactorum culmorum oxysporum solani in mg / l f.pisi Cl2CH-CH-SO2 - # - Cl b) 100 0 0 0 0 0 0 0 0 # Cl Cl2CH-CH-SO2 - # - F b) 100 0 0 0 0 0 0 0 0 # Cl Example B: Mycelium growth test Nutrient medium used: 20 parts by weight of agar agar 200 parts by weight of potato decoction 5 parts by weight of malt 15 parts by weight of dextrose 5 parts by weight of peptone Ratio of solvent to nutrient medium: 2 parts by weight of acetone 100 parts by weight of agar medium specified amount of solvent. The concentrate is thoroughly mixed in the stated proportions with the liquid nutrient medium cooled to 42 ° C. and poured into Petri dishes with a diameter of 9 cm. Furthermore, control plates are set up without adding any preparation.

If the culture medium is cold and solid, the plates are filled with the in The mushroom species indicated in the table are inoculated and incubated at about 21 ° C.

The evaluation is carried out after 4 to 10 days, depending on the rate of growth of the fungi. During the evaluation, the radical mycelial growth on the treated culture media is compared with the growth on the control culture media. The fungal growth is rated using the following key figures: 0 no fungal growth 1 very strong growth inhibition 2 moderate growth inhibition 3 weak growth inhibition 4 growth equal to the untreated control active ingredients, active ingredient concentrations and results are shown in the following table: Test fungi and bacteria Active ingredients concentra- Mycosphaerella Colletotrichum Phialophora Pircularia Xanthomonas tion ppm musicola coffeanum cinerescens oryzae oryzae CO # # # NS-CCl3 10 3 0 3 4 4 # # CO (known) CCl3-CH-SO2-C5H5 10 0 - 0 0 - # Cl Cl3C-CH-SO2-C4H9-n 10 0 2 3 0 - # 5 0 - - 0 - Cl Cl3C-CH-SO2-CH3 10 0 0 0 0 1 # Cl 5 0 - 2 0 - Continued Table Mycelium Growth Test Fungi and Bacteria Active ingredients concentra- Mycosphaerella Colletotrichum Phialophora Pircularia Xanthomonas tion ppm musicola coffeanum cinerescens oryzae oryzae Cl3C-CH-SO2 - # - Cl 10 0 0 1 0 - # 5 0 - - 0 - Cl Cl3C-CH-SO2- # 10 0 0 2 0 - # 5 0 - - 0 - Cl Cl2CH-CH-SO2 - # - Cl 10 0 0 0 0 0 # 5 0 0 0 0 0 Cl Cl2CH-CH-SO2- # 10 0 0 0 0 0 # 5 0 0 2 0 1 Cl Example C: Seed dressing test / wheat stone brandy (seed-borne mycosis) To produce an appropriate dry dressing agent, the active ingredient is stretched with a mixture of equal parts by weight of talc and kieselguhr to form a finely powdered mixture with the desired active ingredient concentration.

Wheat seeds are contaminated with 5 g of Tilletia chlamydospores tritici per kg of seed. For dressing, the seeds are shaken with the dressing agent in a sealed glass bottle. The seeds are placed on damp clay under a Top layer of a layer of cheesecloth and 2 cm moderately moist compost soil for 10 days exposed to optimal germination conditions for the spores in the refrigerator at 100C.

The germination of the spores is then determined microscopically the wheat kernels, each with around 100,000 spores. The active substance is more effective, the fewer spores are germinated.

Active ingredients, active ingredient concentrations in the seed dressing, seed dressing application rates and germ percentage of the spores are shown in the following table: Table seed dressing test / wheat stone brandy Active ingredients active ingredient seed dressing spore Concentrated effort germination tion in abundance in, ' Dressing g / kg seed in weight good unpickled - -> 10 S. CH2-NEi-C-9, io 5 / 10 1 5 CH2-NH-C- S. (known) CCl3-C, H-SO2-C2H 10 1 0.05 Cl Cl3C-CH-SQ-C4H-n 10 t 0.5 cl C} G-eH-SQa -Ol Ql 10 1 0.005 Cm 3 1 0.5 O13g-H-SOt 10 1 often05 Cl X1nC-GH-SQ2 <10 1, es25 Cl 3 1 0.5 Continuation of the table of seed dressing test / wheat stone brandy Active ingredients active ingredient seed dressing spore concentrated effort germination tion in quantity in * Dressing g / kg seed in aew-.4 good Cl2CH-C, H-SO2 10 1 0.005 Cl C12CH-CH-SO2-P 10 1 0.5 C1 Example D: Seed dressing test / strip disease of barley (seed-borne mycosis) To produce a suitable dry dressing agent, the active ingredient is stretched with a mixture of equal parts by weight of talc and kieselguhr to form a finely powdered mixture with the desired active ingredient concentration.

For dressing, barley seeds are shaken by Helminthosporium gramineum is naturally contaminated with the pickling agent in a sealed glass bottle. The seeds are placed on moist filter discs in sealed Petri dishes in the refrigerator for 10 days at a temperature of 40C. This will germinate the barley and possibly also the fungal spores. Then sows the pre-germinated barley with 2 x 50 grains 2 cm deep in Fruhstorfer standard soil and cultivated them in the greenhouse at temperatures around 180C in seed boxes that daily 16 hours of exposure to light. Form within 3 to 4 weeks the typical symptoms of streak disease.

After this time, the number of diseased plants is determined in percent of the total number of emerged plants. The active ingredient is the more effective, the less Plants are diseased.

Active ingredients, active ingredient concentrations in the dressing, amounts of dressing applied and the number of diseased plants are shown in the table below: Table of seed dressing test / snow mold / barley streak disease Active ingredient active ingredient seed dressing number of strips concentration in the application rate of diseased plants in Dressing agent in in g / kg seed-% of the total Weight; well-run plants unpickled - - 47.8 S. CH2-NH-CS \ 75 2 28.4 in 30 2 38.1 CH2-NH-CS S. (known) CC13-C, H-SO2-C2H5 30 2 6.9 Cl Cl3C-CH-SO2-C3H7-n 30 2 5.2 Cl Cl3C-CH-SO2-C4Hg-n 30 2 1.1 C1 Cl3C-CH-SO2-CH3 30 2 2.3 61 Example E: Seed dressing test / snow mold (seed-borne mycosis) To produce a suitable dry dressing agent, the active ingredient is stretched with a mixture of equal parts by weight of talc and kieselguhr to form a fine-powdered mixture with the desired active ingredient concentration.

For dressing, rye seeds are shaken, which are obtained by Fusarium nivale is naturally contaminated with the pickling agent in a sealed glass bottle. The seeds are placed 1 cm deep in Fruhstorfer standard soil with 2 x 100 seeds in seed boxes sown.

In climatic chambers at 100C, 95% relative humidity and more diffuse The young plants develop and show within the daylight illumination first 3 weeks the typical symptoms of the son's mold.

After this time, the number of fusarium plants in Percent of the total emerged plants.

The active ingredient is the more effective, the fewer plants are diseased.

Active ingredients, active ingredient concentrations in seed dressing, seed dressing application rates and number of diseased plants are shown in the following table: Table seed dressing test / snow mold Active ingredient con-dressing agent on number of fusarium concentration in the wall quantity in plants in% of Dressing agent in g / kg total seed Weight-4 running plants unpickled - - 21.2 S. CH2-NH »C-Ss n '30 2 9.7 CH2-NH-eS 5 (known) Cl3C-CH-SO2-C4z9-n 30 2 4.5 Ci Cl3C-CH-SO2-CH3 3Q 2 7.6 Cl Example F: Soil Treatment Agent Test / Soil-borne Mycoses To produce an appropriate preparation of the active ingredient, the active ingredient is stretched with talc to 5% and then with quartz sand to a 0.5% active ingredient content.

The active compound preparation is mixed evenly with Fruhstorfer Standard soil, which is first sterilized and then with pure cultures of the test mushrooms has been vaccinated. The soil is filled into pots and filled with 5 x 10 seeds of the host plant sown.

The pots are placed in the greenhouse at the specified temperatures and kept normally moist.

The number of healthy plants is determined 3 weeks after sowing as a percentage of the seeds laid out. O% means that no healthy plant has grown is, 100% means that healthy plants have emerged from all seeds.

Active ingredients, active ingredient concentrations in the soil, test mushrooms, host plants, greenhouse temperatures and results are shown in the following table: Table Soil treatment agent test / soil-borne mycosis Rhizoct. Fusarium Test mushrooms: solani culmorum Host plant: pea pea Temperature range: 18 - 22 ° 22 - 25 ° Active ingredient conc. in Active ingredients mg / liter of soil Frühstorfer unit earth serilized, untreated - 100 92 Frühstorfer unit earth serilized and inoculated, untreated - 0 10 S. # CH2-NH-CS # # # Zn 100 2 2 # # CH2-NH-CS # S. (known) CCl3-CH-SO2-C2H5 100 45 75 # Cl Cl3C-CH-SO2-C3H7-n 100 60 # Cl Continuation of the table Soil treatment agent test / soil-borne mycosis Fusarium Test mushrooms: culmorum Host plant: pea Temperature range: 22 - 25 ° Active ingredient conc. in Active ingredients mg / liter of soil Cl3C-CH-SO2-C4H9-n 100 60 # Cl Cl3C-CH-SO2 - # - Cl 100 65 # Cl Cl3C-CH-SO2-CH3 100 65 # Cl Cl3C-CH-SO2- # 100 65 # Cl Example G: Microbicidal Effect / Reciprocal Sprout Inhibition Values The table shows the reciprocal sprout inhibition values for some selected species from the three groups bacteria, fungi and yeasts. This expresses the dilutions of the compounds mentioned at which the growth of the selected microorganisms is completely inhibited when these compounds are added to a nutrient medium that is optimal for the organisms. The microorganisms used for this liemmungstest are widespread and known to be resistant to conventional chemical preservatives and disinfectants.

The listed germ inhibition values are determined according to the usual dilution method determined as follows: The specimens to be tested are in the specified below Diluent prepared in various concentrations.

In the prepared, filled with standardized nutrient substrates Test tubes are given certain amounts of the pre-dissolved preparations.

All work is carried out under aterile conditions.

The incubation of the various microorganisms given in the table takes place at 300C.

The sprout inhibition values given in the table show the concentrations at which no growth occurs yet.

Thinner: ethylene glycol Table microbicidal effect / reciprocal germ inhibition values Active ingredient Asper- Penicil- Paecillo- Candida Saccha- Bact. Escehri- gillus lium myces albicans romyces proteus chia tereus camerun- var. spec. coli ense Cl3C-CH-SO2-C4H9-n 72,000 72,000 72,000 72,000 72,000 # Cl Cl3C-CH-SO2-CH3 50,000 72,000 50,000 72,000 72,000 15,000 12,000 # Cl Cl3C-CH-SO2 - # - Cl 48,000 48,000 60,000 72,000 50,000 # Cl Cl2CH-CH-SO2 - # - Cl 24,000 48,000 48,000 48,000 72,000 15,000 15,000 Example H: Microbicidal Action / Tanning Agent Solution Natural tanning agents are protected against fungal growth by adding the active ingredients, as can be seen from the following table; the concentration data relate to the active ingredient.

This is distributed in the solvent specified below, the tanning solution added and brought to the concentrations shown in the table.

The data relate to g active ingredient per liter of solvent.

In the table: - no mold growth + mold growth Solvent: Ethylglycol Table Microbicidal effect / tannin solution Active ingredient concentration fungal growth g / l Control - + o-oxydiphenyl 1 + (known) 5+ 10 C13C-CH-SO2-C4H9-n 0.1 Cl 0.5 C13C-CH-So2-CH3 0.1 Cl 0.5 Cl3C-C, H-SO2Cl 0.1 Cl 0.5 Example I: Microbicidal Action / Wood Pulp Preservation To carry out the experiments, wood pulp with the water content given in the table was treated with the active ingredients listed in various concentrations.

Pieces 2 x 2 cm in size were placed on nutrient media inoculated with mushrooms and incubated, then the zones of inhibition were measured. In addition, 10 x 10 cm large pieces buried in soil and the degree of rotting after 3, 6 and 10 weeks observed.

Refer to the concentrations given in the table below focus on the dry weights.

The numerical values given under the heading "Degree of rotting" mean: O no visible rotting 1 moderate mold infestation 2 severe mold infestation 3 complete rotting Table Microbicidal effect / wood pulp preservation Water content of the wood pulp: 50% Active ingredient concentration inhibition zones in mm degree of rotting tration Asper Penicil 3 week 6 week 1 week gillus lium terreus camerun- ense Control O 0 1-2 2 2 Phenyl mercury 0.01% 0-0.1 0-4 2 2 2 acetate 0.05% 3-4 0-3 1-2 2 2 (known) 0.2% 7 9-11 1-2 2 2 0.8% 5-9 15-16 1 1-2 2 0.01% 4 1 1-2 2 2 Cl3C ~ CH-SO2-CH3 0.05 * 20 10 1 2 2 Cl 0.2,> 30 25 1 1 1 0.8 ffi>30> 30 0 1 1 0.01% 2 0 1-2 2 2 Cl3C-CH-SO2Ol to-C1 0.05 * 12 3 1 1 2 Cl 0.2 *>30> 30 1 1 1 0.8%>30> 30 0 1 1 Example K: algicidal effect Chlorella and Oscillatoria are grown on solid nutrient substrates. The effectiveness of the active ingredients is checked in the inhibition zone test and indicated by the wach inhibition. The zones of inhibition are measured in mm.

Scenedesmus is grown in a liquid nutrient substrate. The effectiveness of the active ingredients is assessed on the basis of the increase in Scenedesmus; it means: + growth - no growth Active ingredients, concentration data, zones of inhibition and assessment of the multiplication can be seen from the following table: Table algicidal activity Active ingredients Concentration inhibition zone in mm increase tration Chlorella Scene- Scenedesmus desmus Control O 0 + Cl3C-CH-S02-C4H9-n 0.1 15 15 - Cl 0.01 7 15 - 0.001 0 1 + Cl3C-CH-S02-C3H7-n 0.1 20 20 - Cl 0.01 8 15 - 0.0G1 0 2 + C13C-CH-S02-CH3 0.1 20 20 - Cl 0.01 5 20 - 0.001 0 5 - Cl3C-C, H-S02Cl 0.1 10 15 - Cl 0.01 5 15 - 0.001 0 3+ Cl3C-CH-S02 4 Q, 1 10 15 - Cl 0.01 8 15 - 0.001 2 3+ Cl2CHCtHS02Cl 0.1 10 15 - Cl 0.01 7 15 - 0.001 0 2+ Example L: Antimicrobial finish / textile material Textiles made from various materials are given an antimicrobial finish by incorporating the active ingredients.

As can be seen from the table, the give on inoculated culture media laid out 2 x 2 cm pieces of inhibition zones, which are measured in mm.

Antimicrobial equipment / textile material table Inhibition zones in mm Active ingredient Material Concentrate Staphylo-Tricho- tration coccus phyton aureus menta- grophytes Control Perlon O 0 Cotton O 0 Wool O 0 Cl3C-C, H-SO2Cl Perlon 0.1 0 Cl 0.25 0 0.5 3 0.75 1 16 1 1.5 20 Cotton 0.1 1 0.25 2 0.5 Q 2-3 0.75 0 12 1 0 17 Wool 0.1 0 0.25 0 0.5 0 o 0.75 1 8 1 2 10 Example M: In vitro test on Psoroptes cuniculi 3 parts of active ingredient are mixed with 7 parts of a mixture of equal parts by weight of ethylene glycol monomethyl ether and nonylphenol polyglycol ether. The emulsion concentrate obtained in this way is diluted with water to the desired application concentration in each case.

With this active ingredient preparation larvae, nymphs and adults brought into contact by Psoroptes cuniculi. For this purpose, 3 ml of the active ingredient preparation pipetted onto filter paper sandwiches, the mites between the filter paper discs brought and stored in Petri dishes for 24 hours.

The effectiveness of the active compound preparation is determined after 24 hours by determining the number of dead mites. The effect is given in%, where 100% means that all mites have been killed and 0 means that all mites Life.

The active substances examined, the concentrations tested, the parasites tested and the results obtained are shown in the following table: Table of in vitro tests on Psoroptes cuniculi 100 fo 50% Active ingredients Effect with an active ingredient concentration in ffi of ClDC-CH-502-CH3 0.03 0.01 Cl Cl3C-CH-SO2- (CH2) 2-CH3 0.003 0.002 3 Cl Cl3C-CH-SO2- (CH2) 3-CH3 0.003 0.002 Cl Cl2CH-CH-SO2 <0.003 0.001 Cl - Cl2CH-CH-SO2 <Cl 0.0003 0.0002 Cl - Example N: Deterrent test / house mouse Test animal: white laboratory mouse (Mus musculus) Active ingredient concentration in the test feed: 0.5 / 'To produce an appropriate active ingredient preparation, 3 parts by weight of active ingredient are mixed with 2.8 parts by weight of highly disperse silica and 4.2 parts by weight of talc. To prepare the test bait, 1.67 parts by weight of this active ingredient concentrate are intimately mixed with 95 parts by weight of a flour-like standard feed commonly used for animal husbandry with the addition of 3.33 parts by weight of methyl cellulose and a little water. 2 spherical bait pellets are formed from 6 g of dry substance and are dried for 24 hours at room temperature before the start of the experiment.

These pellets are placed in 2 white laboratory mice kept together without additional feed for 24 hours before. Water is freely available. the Remnants of the pellets are dried back after the end of the test and weighed.

The reweighed residual amount, expressed as a measure of the deterrent effect, is used as a percentage of the amount originally used.

100% quenching means nothing at all from the pellets has been eaten.

The active ingredients, the number of experiments and the results are shown in the table below: Table of deterrent test / house mouse Active ingredient number of deterrents in% Single tests (mean) Tetramethylthiuram = disulfide 3 67.8 (known) ClDC-CH-S02-C3H7-n3 81.7 cl 3.2 <3 82.7 Cl 3, 2 <Cl 1 is, 3 Cl Cl2CH-CH-S02 <97s7 Cl Cl2CH-CH-SO2 to F2 80.9 Cl Preparation examples: The previously known compounds 1,2,2,2-tetrachloroethyl-methylsulfone, 1,2,2,2-tetrachloroethyl-ethyl-sulfone and 1,2,2,2-tetrachloroethyl-phenyl-sulfone can be prepared according to the literature.

The following new compounds can be produced in a corresponding manner: Example 1: 76.8 g (0.3 mol) of 1,2,2,2-tetrachloroethyl-butyl- sulfide and lets the approach stand overnight. The next day the solvent is evaporated in vacuo. The oily residue is taken up in methylene chloride and washed several times with water. After the solution has been dried over sodium sulphate, the solvent is evaporated off and the residue is distilled at a boiling point of 0.02 / 134 ° C. Yield: 47 g (54% of theory) 1,2,2,2-tetrachloroethyl-butyl-sulfone; Refractive index nD20 = 1.5208.

(The precursor was obtained from 220 g (1.5 mol) of chloral in 300 cc of ethyl ether with the dropwise addition of 135 g (1.5 mol) of n-butyl mercaptane at a temperature of 5 to 100 ° C. The solution was obtained at room temperature for a few hours and then added dropwise to a suspension of 310 g (1.5 mol) of phosphorus pentachloride in 400 cc of ethyl ether at -15 to -100 ° C. The batch is stirred for 3 hours at room temperature and then the solvent is evaporated off in vacuo / 970C. Yield: 266 g (64% of theory) 1,2,2,2-tetrachloroethylbutyl sulfide; refractive index n20 = 1.5172.) The following compounds were also prepared in an analogous manner: Example 2: The compound is obtained in 43.5 yield.

Melting point 74 ° C.

Example 3: The compound is obtained in a 70% yield.

Melting point 70 ° C.

Example 4: The compound is obtained in 73% yield, melting point 77 ° C.

Example 5: The compound is obtained in a 55% yield.

Melting point 980C.

Example 6: The compound is obtained in 25.5% yield.

Melting point 93 ° C.

Claims (1)

Patent claims: 1) Fungicidal, bactericidal and acaricidal agents and deterrents against rodents and ruminants, characterized by a content of trichloro and tetrachloroethyl alkyl sulfones or trichloro and tetrachloroethyl aryl sulfones of the formula in which X stands for hydrogen or chlorine and R stands for alkyl with up to 6 carbon atoms and for aryl, where the latter can be substituted one or more times by halogen, trifluoromethyl, alkyl with up to 4 carbon atoms and / or nitro groups. Use of trichloro and tetrachloroethyl alkyl sulfones or trichloro and tetrachloroethyl aryl sulfones according to Claim 1 for combating fungi, bacteria and mites and for deterring rodents and ruminants. Trichloro- and tetrachloroethyl-alkyl-sulfones or trichloro- and tetrachloroethyl-aryl-sulfones of the formula in which X stands for hydrogen or chlorine and R stands for alkyl with 5 to 6 carbon atoms and for aryl which is monosubstituted or polysubstituted by halogen, trifluoromethyl, alkyl with up to 4 carbon atoms and / or nitro groups.