DK166063B - USE OF 3-AMINO-1,2-BENZISOTHIAZOLES AS MICROBICIDES TO PROTECT TECHNICAL MATERIALS - Google Patents

Abstract

1. Use of 3-amino-1,2-benzisothiazoles of the formula see diagramm : EP0146774,P4,F2 in which R**1 denotes optionally substituted C1 -C6 - alkyl, phenyl or benzyl and R**2 denotes hydrogen, halogen or optionally substituted C1 -C6 - alkyl, C1 -C6 - alkoxy, phenyl or benzyl, as the active compounds in microbicidal agents for protecting industrial materials.

Description

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DK 166063 B

The invention relates to the use of 3-amino-1,2-benzisothiazole as active substances in microbicidal agents for the protection of technical materials.

3-Amino-1,2-benzisothiazoles and their use as antimycotics are known from DE Publication No. 2,803,755.

It has now been found that 3-amino-1,2-benzisothiazoles of formula I

10 c f ^ Ys \ N (I) NHR1 wherein 15 R 1 means (1

Unsurprisingly, the 3-amino-1,2-benzisothiazoles of the present invention can be used to protect technical materials because of an action against plant, veterinary and human pathogenic fungi (DE disclosure no. 1,545 .844) cannot be attributed to an effect against the completely different microorganisms on technical materials.

C 1-6 alkyl means a straight or branched hydrocarbon group having 1 to 6 carbon atoms. For example, are mentioned methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl and isohexyl. Preferred lower alkyl groups are methyl and ethyl.

For example, mention is made of 3-ethylamino-benzisothiazole.

of)

The preparation of 3-amino-1,2-benzisothiazoles is known by itself. It occurs by reaction of the corresponding 3-chloro-1,2-benzisothiazolium chlorides with ammonia, cf.

Chem. Ber. 90, 2566 (1966). However, they can also be prepared by reacting 3- [1,2-benzisothiazolyl- (3) J-imino-1,2-35-benzodithiols with primary amines, cf. DE Publication No. 2,803,755.

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Technical materials according to the invention are non-living materials prepared for use in the art.

Technical materials which are to be protected from the microbial alteration or destruction of the active substance of the present invention can, e.g. such as adhesives, adhesives, paper and cardboard, textiles, leather, wood, iron and plastic products, refrigerants and other materials that can be broken down by microorganisms. Among materials to be protected, 10 must also be mentioned parts of production plants, e.g. cooling water circuits that can be bothered by microorganisms. Within the scope of the present invention, preferably, as technical materials, adhesives, adhesives, paper, cardboard, leather, wood, ironing agents, refrigerant lubricants and refrigeration circuits should be mentioned.

As microorganisms which can cause a breakdown or change of technical materials, e.g. These include bacteria, fungi, yeasts, algae and mucus organisms. The substances of this invention preferably act against bacteria, molds, especially fungi that discolor and destroy wood (basidiomycetes), as well as against mucus organisms and algae.

For example, are mentioned microorganisms of the following genera:

Alternaria, such as Alternaria tenuis, Aspergillus, such as Aspergillus niger,

Chaetomium, such as Chaetomium globosum,

Coniophora, such as Coniophora puteana,

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

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The active substances of the present invention can be converted into conventional preparations / such as solutions / emulsions, suspensions, powders, pastes and granules according to the field of application.

These can be manufactured in a manner known per se, e.g. by mixing the active substances with a surfactant consisting of liquid solvents and / or solid carriers, optionally using surfactants such as emulsifiers and / or dispersants, e.g. by using water as an excipient, organic solvents such as alcohols may optionally be used as auxiliary solvents.

Organic solvents for the active substance may e.g. be alcohols such as lower aliphatic alcohols, preferably ethanol or isopropanol, or benzyl alcohol, ketones such as acetone or methyl ethyl ketone, liquid hydrocarbons such as gasoline fractions, or halogenated hydrocarbons such as 1,2-dichloroethane.

The microbicidal agents usually contain the active ingredient in an amount of 0.5-95% by weight, preferably 5-80% by weight.

The concentration of use of the active substances herein depends on the nature and occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimum amount of use can be determined by test series. Generally, the application concentrations are in the range of 0.001-5% by weight, preferably 0.001-0.5% by weight, based on the material to be protected.

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The present active substance may also be present in admixture with other known active substances. For example, the following active substances are mentioned:

Benzyl alcohol mono (poly) hemiformal and other formaldehyde cleavage compounds (e.g. hexahydro-s-triazines), benzimidazolylmethylcarbamates, tetramethyl-thiuram disulfide, zinc salts of dialkylthiocarbamates, 2,4,5,6-tetrachloroiso-

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4 phthalonitrile, thiazolylbenzimidazole, mercaptobenzthiazole, trialkyltin compounds, methylene bisthiocyanate and phenol derivatives such as 2-phenylphenol, (2,2 * -dihydroxy-5,51-dichloro) -diphenylmethane and 3-methyl-4-chloro-phenyl

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Preparation.

Example 1 300.4 g (1.0 mole) of 3- [1,2-benzisothiazolyl- (3) J-imino-10,2-benzodithiol, 157.8 g (3.5 mole) of ethylamine and 10 g sodium methylate is suspended in 2.0 liters of a 1: 1 methanol-ethanol mixture and then heated to 150 ° C for 6 hours in an autoclave. Then, remove the solvent in vacuo and dissolve the residue in 500 ml of Ί5 concentrated hydrochloric acid. This solution is diluted with 500 ml of water and the precipitated product is separated by shaking with ether. The clear aqueous solution is made basic by adding sodium hydroxide solution and the released base is taken up in ether. 200 g of crude base are obtained which are purified by vacuum distillation. Yield: 160-180 g (45-50%) of 3-ethylamino-1,2-benzisothiazole.

Examples of Use 25 Example 2

To detect the effect against fungi, the minimum inhibitory concentration (MHK) of the present active substance of Example 1 is determined.

To an agar prepared from Beer yeast and peptone 30, the present active substance is added at concentrations of 0.1 to 5000 mg / liter. After solidification of the agar, graft cultures are seeded with the microorganisms listed in the table.

After 2 weeks of storage at 28 ° C and 60-70% * s relative humidity, MHK is determined. MHK is the lowest concentration 35 of active substance at which no overgrowth occurs with the microorganism used, and it is listed in the following table. As a comparative compound, N-cyclohexyl-N-methoxy-2,5-dimethyl-3-furamide is used (U.S. Patent No. 3,993,772).

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Table in "MHK in mg / liter

Together-

Active equation 5 Experimental organisms_ substance_ compound

Alternaria tenuis 15

Aspergillus niger 50 ^> 5000

Chaetomium globosum 35 100 10 Coniophora puteana 50 0/5

Lentinus tigrinus 5 3.5

Penicillium glaucum 20> 5000

Polyporus versicolor 10> 5000

Aureobasidium pullulans 20 200 15 Sclerophoma pityophila 2 3500

Trichoderma viride 200 2000

It is clear that the active substance of the present invention is clearly superior to the active substance of the commercial, especially as regards the width of the spectrum of effect.

Example 3

Effect against mucus organisms.

The compounds of this invention, dissolved in a little acetone, are used at concentrations of 0.1-100 mg / liter in Allen's nutrient solution (Arch. Microbiol. 17, 34-53 (1952)). 4 liters of sterile water contains 0.2 g of ammonium chloride, 4.0 g of sodium nitrate, 1.0 g of potassium hydrogen phosphate, 0.2 g of calcium chloride, 2.05 g of magnesium sulfate, 0.02 g of iron chloride, and 1% caprolactam. Briefly, the nutrient solutions are seeded with mucus organisms (about 10 g / ml) isolated from spin water circuits used in polyamide preparation. Nutrient solutions containing the minimum inhibitory concentration (MHK) or higher concentrations of active substance, after 3 weeks of culture at room temperature, are still completely clear, i.e. the strong propagation of micro-organisms.

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6 organisms and mucus formation observed after 3-4 days in nutrient-free nutrient solutions are absent.

For the active substance of Example 1, an MHK of 75 mg / liter can thus be determined.

Example 4

Determination of the toxic limit values (kg / m3 of wood) of active substances for Coniophora puteana respectively. Polyporus 10 versicolor on pine tree respectively. Beech.

The toxic limit values are determined according to that of H.P. Sutter, Int. Biodeterioration Bulletin ΊΛ (3), 1978, pages 95-99, described method.

Each time, freshly cut single-piece pieces (size 40 x 40 mm, thickness about 2 mm) are used for the samples, which are soaked in vacuum with solutions of different concentration of active substance. With a solvent concentration, 15 wood samples are soaked at a time each time.

Of these, each time 5 is used simultaneously for a mycological sample.

The amount of the absorbed active substance is determined from the solvent retention (which is determined by weighing the piece of wood before and after the impregnation), the density of the wood and the concentration of the active substance in the residual impregnating solution.

25 Prior to the mycological specimen, the specimens were sterilized with propylene oxide and each 1 specimen placed in a petri dish in contact with the fully developed mycelium of the fungus used on malt extract agar. After 6 weeks at 21-23 ° C, the toxicity limits are visually determined.

30 The following table lists the toxicity limits (kg / cm3 of wood) for the compounds studied. The toxicity limits are those concentrations where the tree is no longer attacked.

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Table II

Toxicity limits (kg / cm3 wood) for active substances against wood-destroying fungi.

Coniophora puteana Polyporus versicolor 5 Beechwood pine active ingredient of Example 1 0.25-0.5 0.2-0.61 BCM + 6.73 5.4 10 - +) Comparative Compound, Benzimidazolylmethylcarbamate (Carbendazine).

Summary of the different effects (minimum 15 inhibitory concentrations (MHK values), mg / liter) of various microbicides used in material protection.

MHK values 20 N-cyclohexyl-3-ethylamide

Damage investigated- -N-methoxy-no-1,2-benzene-microorga-2,5-dimethyl-isothiazole nismer BCM + -3-furamide + + + ++ ++ Funoi imoerfecti

Aspergillus niger 5 5000 50

Penicillium glaucum 0.25 5000 20

Sclerophoma pityophila 0.1 3500 2

Basidiomvceter 30 Coniophora pureana 2000 0.5 50

Lentinus tigrinus 1000 3.5 5 S1imorqan ismer

Mucus bacteria inactive 100 75 prepared by K. Kato, 35 Chem. Ind. (1962), page 1146.

+) Benzimidazolylmethylcarbamic acid methyl ester ("Mergal BCM" from Riedel de Haen, "Preventol BCM" from Bayer AG).

40 ++) Active substance in "Xyligen B" from BASF.

+++) Active substance according to Example 1.

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Explanation of the experiments.

The determination of the effect (minimal inhibitory concentration) against fungi imperfecti and basidiomycetes is made as described in Example 2, and the determination of the action 5 (MHK) against mucus organisms is made as described in Example 3.

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Claims (2)

Use of 3-amino-1,2-benzisothiazoles of formula O, NHR 10 wherein R1 represents C1-6 alkyl as active substances in microbicidal agents for the protection of technical materials. Use according to claim 1, characterized in that the microbicidal agents contain 0.5-95% by weight 15 of the active substance. 20 25