SU346834A1 - - Google Patents

Description

This invention relates to new microbicidal agents used to combat damaging or destructive organic materials and household items. In particular, the invention relates to microbicidal agents for combating microorganisms that damage and destroy cellulose or cellulose-containing materials, as well as destructive dyes.

A number of microbicidal active principles for the protection of organic materials are known, many of which do not fully meet the requirements. For example, they are often used to combat cellulose-damaging or killing cellulose-containing materials, phenols, especially pentachlorophenol, or trialkyloxy. tin, especially tributyl oxyl tin, can only be used limitedly due to high vapor pressure, an unpleasant odor, insufficient light resistance, etc. Although these active principles have a wide spectrum of action, their duration of action is unsatisfactory. Benzene substituted in the nucleus of benzene by one or several chlorine atoms. The imidazoles are still described as herbicides, insecticides, acaricides and nematocides and as active against the control of keratin-absorbing insects. Products containing chlorobenzimidazole or a mixture of such iolichlorobenzimidazoles that are chlorinated in the benzene core at least twice as active as iachal are suitable for controlling harmful substances.

or microorganisms that destroy organic materials and household items. The active substances of the first-time agents or mixtures of active principles are inhibited and prevent the growth of bacteria,

fungi and yeast, in particular, destroying and damaging cellulose and cellulose-containing materials. These polychlorobenzimidazoles have a wide spectrum of action, are significantly stable with respect to

to moisture of air and exposure to light, have a very good affinity with these materials and long-lasting effect. Due to these properties, as well as lower vapor pressure, good light fastness and no odor, these products are suitable for imparting microbicidal properties to small paints, varnishes, firns, wood, wood and textile materials.

It is proposed to use as a microbicide a compound of the general formula

//

H „„.

C-C1

Hh

where X is chlorine, an is an integer of at least two.

The following nichlorobenzimidazoles are preferred as preferred microbicidal active principles: 2,5,6-trichlorobenzimidazole, 2,4,5,6-tetrachlorobenzimidazole, 2,4,5,6,7-pentachlorobenziM | Idazole, and also mixtures of these nichlorobenzimidazoles, the preferred percentage the composition of which is given below.

Blend ab

2,5,6-Trichlorobenzimidazole42,6,4,4

2,4,5,6-Tetrachlorobenzimidazol29, 7 33.8

2,4-5,6,7-Peitachlorobenzimidazole 27, 7 61.8

The preparation of these compounds is known from Swiss patent No. 443777. It also describes the preparation of individual components, as well as mixtures, by chlorinating 2-mercantobenzimidazole in water. Mixtures a and b are obtained by an improved method if 2,5-dichlorobenzimidazole is chlorinated in the presence of ferric chloride in glacial acetic acid with the addition of base. During the removal procedure, the addition of chlorine is stopped several times and the acidity of the reaction mixture lowers the addition of base, for example sodium acetate. Chlorination practically remains at the stage of mixtures a and b. Both mixtures can be separated by fractional crystallization. The mixtures have uniform melting points.

When using new products, the processed materials get good microbicidal properties. Since the active substances are odorless, they are particularly suitable for treating materials that are located in closed rooms, such as wood, paper, paints, etc. Processed materials, such as paper, do not show any color change during prolonged exposure. Compared with tributyl tin, polychlorobenzimndazoles are practically non-volatile. When stored for 16 days at a temperature of 90 ° C, the weight loss of tributyloxyl tin is an example, about 34%; the weight loss of the mixture of a polychlorobenzyl Jidazole is only 0.4%.

The proposed microbicidal agents are liquid (solutions.

emulsifiable concentrates) or paste-like concentrates of the active substance, they can be diluted to the required concentration immediately before use. Since the active principles are soluble in organic solvents, they are suitable for non-aqueous applications. Polychlorobenzimidazoles form a salt with alkali metal ions and therefore they can be used in the form of aqueous dispersions or diluents. The processing of wood and wood materials by new means is thus greatly simplified.

Experiments were conducted to determine the bactericidal and fungicidal actions of the proposed polychlorobenzimidazoles.

I. Range Experience. The active start solution is mixed with the still hot nutrient agar. The agar is then poured into olives and after hardening, the experienced buds are wiped.

Applicable test microorganisms

A. Bacteria: Escherichia coli, Bacillus pumilus, Sarcina ureae. Bacillus subtilis, Sacrina iutea. Streptococcus faecalis, Staphylococcus saproph., Staphylococcus aureus, Corynebacterium diphteroides 17, Brevibacierium ammoniogenes. Salmonella pullorum, Proteus vulgaris HXL, Proteus vulgaris ox 19, Proteus mirabilis.

B. Mushrooms:

1. Aspergillus niger, Penicillium italicum, Fusarium oxysporum, Candida albicans, Stemphylium botryosum.

2. Cellulose destructors: Chaetomium globosum, Trichoderma viride, Metarrhizum glutinosum, Stachybotrys atra.

3. Yeast: Saccharomyces cerevisiae Torula utilis, Monilia nigra.

4. Dermatophytes: Trychophyton gypseum Ctenomyces spec., Keratinomyces ajelloi, Epidermophyton flossosum.

5. Ubiquitous saprophytes: Rhizopus nigricans, Paecilomyces varioti, Penicillium citrinum, Aspergillus oryzae, Aspergillus clavatus, Aspergillus flavus.

6. Improved mushrooms: Scopulaziopsis brevicaulis, Alternaria tenuis, Acrostalagmus cinnabarinus.

7. House rot: Coniophora cerebella, Poria vaporaria, Poria incarnata.

8. Birds rot: Polystitus versicolor, Daedalea quericina, Lenzites abietina, Lentinus lepideus.

9. Parasites: Fomes annosus.

10. Color-changing mushrooms: Scopularia phyomyces, Pullularia pullulans.

In tab. 1 shows general information about the conditions of the experiments.

Table 1

The limiting concentration of inhibiting growth of various microorganisms is determined.

In tab. 2 shows the bacteriostatic effect, and in table. 3 - fungistatic effect of polychlorobenzimidazoles on some of the above test microorganisms (the numbers indicate the maximum concentration in parts per 1 million).

Table 2 The following were used as active principles: 1.2,5,6-Trichlorobenzimidazole; 2.2,4,5,6,7-Pentachlorobenzimidazole; 3. A mixture of a specified composition; 4.2,4,5,6-tetrachlorobenzimidazole; 5. A mixture of the specified composition. Ii. Testing of braking zones According to the method of drawing or fular, solutions with different contents of the active principle on paper rotundas are used. Ethylene glycol monomethyl ether is used as a solvent, and so-called two-layer agar tiles are used as nutrient agar. They consist of a bactoagar layer and an agar layer suitable for the respective test organisms. The second tile is poured in advance by experienced buds. The rotunda with the active principle then lay on the tiles and incubated for 24 hours at 37 ° C. After that,

Table 3

10 tablespoons of test organisms on the rotunda and under the tons. Test organisms Bacteria: staphylococcus aureus (nutrient agar + potassium tellurite) Escherichia coli (nutrient agar). Fungi: Aspergillus niger (Wort agar) Candida albicans (Wort agar). Table 4 All active principles were applied at a concentration of 0.1%. Symbols in the tables indicate - no action, the cover corresponds to the control; + + weak action, 20-25% of the control cover; + + + Full action, no cover. Iii. Disinfection Experience According to the method of drawing (fular), solutions with different contents of the active principle on paper rotunda are used. The test samples are poured with a lot of suspensions (a physiological solution of sodium chloride with a 10% content of broth) of various test organisms. After that, rotunda are incubated in a humid chamber for 24 hours 40 at 37 ° C and then washed out in 20 ml of physiological sodium chloride solution (containing polyoxyethylene sorbitan monooleate to block the active principle). From this solution, 45 lobes that are removed without a residue are removed and wiped on proper nutrient media. Nutrient medium then incubated for 24 hours at 37 ° C. Table 5 50 5 10 15 20 25 30 35

Vi. Microbicidal experience in small paints.

X parts of the active principle are first dissolved in 5 parts of a mixture of dimethylformamide and ethyl glycol polymethylether (1: 1) and homogeneously mixed with (90-X) parts of polyvinyl acetate ethyl acrylate copolymer-based dispersion paint and 5 parts of water to get ready for application paint. Filter paper covered with paint, which is dried at room temperature for three days. After that, the test samples are blown for eight days in a wind tunnel at 65 ° C and relative humidity. After this, the number of living embryos is determined compared to the control. The results are shown in Table. 5. IV. Experience on urea-destroying microorganisms In one flask (connected to another flask) for powder, a paper rotunda is inserted and filled with a suspension of germs consisting of a liquid urea culture medium and bacteria that destroy urea. 0.1 and are added to the other vial. hydrochloric acid. After that, the flasks are incubated on the tricycle stand for three days at 28 ° C. Then the amount of ammonia produced by the cleavage of urea is determined on the basis of the RP displacement. The following test organisms are used: Brevibacterium ammoniogenes, Proteus ox 19. The proposed polychlorobenzimidazoles prevent the growth of such bacteria in a concentration from 0.05 to 0.1%. It was impossible to establish a change in pH to 0.1 n. hydrochloric acid absorbed in ammonia. V. Experiments with wetting spots. On sterile Vort-agar tiles, paper rotundas are applied to which solutions of active principles have been applied using the fular method, and they are poured in with suspension of germs of test organisms. After that, rotunda are incubated for three days at 28 ° C and relative humidity of 75-85%. The growth on and under the test specimens is then determined. Penicillium expansum, Aspergillus niger, Alternaria tenuis are used as test organisms. In tab. 6 shows the fungicidal action at various concentrations of the active principle. Table 6 air 80-90%. The test samples are then cut and lay on the agar tiles (covering the mushrooms from the top, bacteria, bottom). A mixture of a is used as the active principle. Applicable test organisms Mushrooms: Pullularia pullulans, Paecilomyces varioti, Penicillium cyclopium, Aspergillus oryzae, Chactomium globosum, Aspergillus niger, Candida albicans (Saburo-agar maltose). Bacteria: Staphylococcus aureus, Escherichia coli (nutrient agar). After that, the tiles are incubated: mushrooms - for seven days at 28 ° C and 70-80% relative humidity; bacteria - for 24 hours at 37 ° C and 60% relative humidity. In tab. Figure 7 shows the concentrations of the active principle inhibiting the growth of microorganisms before blowing and after blowing. Table 7 Tin tributyloxyl, even at a concentration of 6%, shows only a partial effect. VII. Experience of protective action against mold pathogens Beech pads and pine sapwood (200 x 10 x 5 mm size) are dried for 14 hours at 105 ° C to determine their dry weight and then weighed. Then, wood samples are impregnated for 24 hours at room temperature and normal pressure with 2.5% and 1% acetone solutions of the active principle and stored for one week at room temperature and pressure conditions. The wood samples are then buried in the soil, so that one third raised above the soil. The beech samples were kept buried for three months, and the pine wood samples were kept for

10 six months in soil containing 23–35% water at 28 ° C and 70–80% relative humidity. After this, the samples were washed under flowing water with a soft brush, dried for 14 hours at 105 ° C, and weighed. The size of the weight loss of the sample indicates the extent to which the wood is protected by active agents against mold pathogens (microorganisms that break cellulose and lignin). The weight loss of a sample of pine wood treated with a 1% solution of mixture a was 6.8% for 6 months, the weight loss of a beech sample (the same treatment) for 3 months was 0.8%. The mixture of chlorinated benzimidazoles protects beech and pine wood from mold (fungi that break down cellulose and lignin) better than penta.chlorphenol, which at a concentration of 2.5% did not act only partially after the expiration of three months on beech wood. Vni. Experience with house rot Wood samples of various tree species are produced for 16–20 hours at 105 ° C to determine the dry weight. After that, the samples are impregnated with the application of vacuum with acetone solutions of the active principle of various concentrations. The second proclamation determines the amount of active principle applied. Next, fill the flasks for the powder to half with quartz sand and 15 ml of nutrient medium, glucose, peptone dissolved in phosphate buffer, and malt extract. A piece of wood, suitable for the growth of a fungus, is put into quartz sand, poured with a fungus culture and incubated for three weeks. On the obtained uniform mushroom turf impose pieces of wood soaked in the active principle. The samples are then kept for two months at 24 ° C and the growth of the fungi and the condition of the wood are determined. After that, samples are blown for four weeks in a wind tunnel at 65 ° C with fresh air and the growth of fungi is determined once again. Conifora cerebella on pine (Pinus silvestris), Coriulus versicolor on beech (Fagus silvatica), Poria incarnata on linden (Filia spec) are used as test organisms. In tab. 8 shows the inhibitory growth of fungi, the concentration of the active principle (in percent). Table 8 To determine the volatility of these substances, a powdered mixture of a is compared with a liquid tin technical bis-butyloxyl and powdered tin technical triphenylhydroxide. The volatility of these substances is expressed in lottery weights in percent, which is obtained if 1 g of the drug is stored in a glass cup in the laboratory at about 20-25 ° C and in a drying cabinet at 90 ° C (see Table 9). Table 9 The following example describes the manufacture of mixtures of lichlorobenzimidazoles. Example. 708 g of 2,5-dichlorobenzimidazol and 2.45 g of iron (III) chloride are stirred up in 5800 ml of glacial acetic acid. The reaction mixture is heated to 40 ° C, cooled and after that 380 g of chlorine is introduced into the mixture at 20 ° C, then heated to 40-50 ° C and 390 g of sodium acetate are added. After the exothermic reaction has subsided, a further e is added; e 380 g of chlorine, then heated again to 45-50 ° C, after cooling 589 g of sodium acetate is added, and more 500 g of chlorine is admitted to the reaction mixture. After standing for one hour, the mixture is poured onto 30 kg of ice and 1500 ml of 30% aqueous sodium hydroxide solution are added so that the mixture has a pH value of 4. The precipitated dough is separated, boiled in methanol and filtered. A mixture consisting of 42.6% 2,5,6 - trichlorbenzimidazole, 29.7% 2,4,5,6 - tetrachlorobenzimidazole and 27.7% 2,4,5,6,7 - pentachlorobenzimidazole crystallizes from the filtrate. having t. pl. 212-214 ° C and containing 54% chlorine. The filter residue is boiled again. once from 1000 l / g of methanol and immediately filtered. Mixture b, consisting of 4.4%: 2,5,6-trichloro benzimidazole, 33.8% 2,4,5,6-tetrachlorobenzimidazole and 61.8% 2,4,5,6,7 - pentachlorobenzimidazole has 280 ° C with decomposition. This mixture contains 59.12% chlorine. , For the protection of materials and especially for the protection of wood, the microbicides offered are used in the form of solutions or emulsions. Wood and wood materials are impregnated or sprayed with such liquid products. The treatment can be carried out outside or with the help of well-known wood impregnation methods. For the manufacture of solutions, preferably organic solvents are used which are practically odorless and non-volatile, for example, mineral oil fractions, tar oils, high-boiling aliphatic and aromatic hydrocarbons, and their chlorinated derivatives, either separately or as mixtures. In order to improve penetration, low-boiling aliphatic hydrocarbons and their derivatives can be added to these solvents. Such solvents are preferred, which, in turn, have an insecticidal action. Organic solvents, dispersants and water are used to make emulsion concentrates. The solvents used are, for example, alcohols, aromatic hydrocarbons, as well as the solvents mentioned. The following substances are used as dispersants: - polyethylene glycol ethers of mono- and dialkylphenols with 5-15 ethylene oxide residues per molecule and 8-9 carbon atoms in the alkyl residue, polyethylene glycol ether fatty alcohols with 5-20 residues of ethylene oxide per molecule and 8-18 carbon atoms in the fraction fatty alcohol, ethylene oxide and propylene oxide condensation products, polyvinylpyrrolidones, urea formaldehyde condensation products, condensation products of sulfonated naphthalene and sulfinated naphthalene derivatives with formaldehyde, naphtha products; di-tertiary acetyl glycols, dialkyldyl auryl ammonium chloride. Solutions and emulsion concentrates contain the active principle, usually in a concentration of 1-80%, preferably 4-10%. Such solutions can be directly applied for. Impregnation, spraying and dyeing of wood and wood-based materials. Emulsion. concentrates are diluted with water before use to form an emulsion with an active content of 4-15%. A microbicidal agent can also be added to other biocidal active principles. Thus, other non-polychlorobenzimidazole agents may contain, for example, 13 insecticides, such as DDT preparations, other fungicides, bactericides, fungistatic agents, and bacteriostatic agents to extend the range of action. If appropriate, these agents may also contain water-repellent substances. To obtain an 8% emulsion concentrate, 8 parts of a mixture, 7 parts of DDT (dichlorodiphenyltrichloroethane), 80 parts of xylene and 5 parts of a combined emulsifier of nonylphenoyl polyethyleneglycol ether and dodecylbenzenesulfonic acid calcium salt are used. The active principle is transported with DDT and dissolved in xylene with the addition of a combined emulsifier. An emulsion concentrate is obtained, which can be diluted with water to the desired concentration. If such aqueous emulsions are coated with wood or wood-based materials, in particular construction wood, then the processed material becomes completely protected from damage by destructive microorganisms. 34683 4 14 To obtain a 4% solution, 4 parts of a mixture are used, 3 parts of DDT preparation, 93 parts of a solvent with an aromatic hydrocarbon content of 93%; boiling range 212-273 ° C, specific gravity 0.930. The active principle is dissolved with the DDT preparation. The resulting solution is applied directly to sprinkle coating or spraying wood and wood-based materials. Subject of the Invention Use as a microbicide of compounds of the general formula where X is chlorine and n is an integer not less than two.