DE1079640B - Process for the production of fungicidal and / or fungistatic masses - Google Patents

Description

GERMAN

The present invention relates to a process for the production of fungicidal and / or fumgistatic masses. According to the invention, water-insoluble metal salts of oxyquinolines are used with water-insoluble metal salts of aliphatic carboxylic acids, naphthenic acids or hydroaromatic Carboxylic acids, in particular of soap-forming carboxylic acids, and with such oxybenzene compounds implemented as a third component that of the general formula. .

OH

Process for the production of fungicides
and / or fungistatic masses

Applicant:

Scientific Oil Compounding Company, Inc., Chicago, 111. (V. St. A.)

Representative: Dipl.-Ing. K. Lengnex, patent attorney,
Hamburg 1, Mönckebergstr. 7th

correspond, where X is a hydrogen, chlorine or bromine atom or a hydroxyl, formyl, nitro, carbaminyl (H ₂ N * CO—), carboxyl, carbalkoxy or carbo-aryloxy group or an alkyl, Represents aryl, alkaryl, aralkyl, alkyloxy or aryloxy radical, η is an integer from 1 to 5, and, if η is greater than 1, the atoms, groups or radicals represented by X are identical or different.

It is already known, metal salts of oxyquinoline to be reacted with metal salts of carboxylic acids, if necessary with the use of phenol-formaldehyde resins. The products obtained in this way are sparingly soluble and for the preparation of solutions solubilizers are required which are not required for the products of the present process are. Also, the new fungus control products are more effective, so they are used in smaller quantities can be applied.

The proportions of the reactants can, if desired, be varied widely will. It can be stoichiometric ratios, but it is preferred as the total amount of water-insoluble Soap and phenol are in a substantial molar excess over the amount of the water-insoluble To apply the metal salt of oxyquinoline. The ratio of phenol to soap can also change can be changed as required.

The reaction temperature can vary widely as desired from temperatures below room temperature can be changed until the reactants begin to decompose. But, to speed it up The use of elevated temperatures is preferred for the reaction.

The products of the process according to the invention can easily be dissolved in one or more of the usual organic solvents including aliphatic solvents such as methanol and acetone, and aroma-Victor Nicholas Kalberg, Skokie, 111. (V. St. Α.),
has been named as the inventor

Table solvents, such as xylene, benzene or toluene, or others obtained from coal tar Solvents, dissolve, also in light petroleum distillates, in oils and oily substances, such as vegetable Oils, fish oils, mineral oils, molten resin and the saturated and unsaturated higher aliphatic Carboxylic acids with 6 to 18 carbon atoms, or in mixtures of these substances. The reaction products also form stable aqueous emulsions. The solutions, dispersions or emulsions obtained can be used as fungicidal and / or fungistatic spraying agents, impregnating agents and coating agents, z. B. in the treatment of canvas, fabric, threads, yarns, ropes, twine, wood, paper, Leather or resins.

Those obtainable by the process according to the invention Masses can e.g. B-. be incorporated into varnishes, fillers, lacquers, paints. Through this the products obtained are made fungus-proof. In phenol aldehyde resins, urea aldehyde resins, melamine aldehyde resins, polymerizable polyester resins, alkyd resins including unsaturated alkyd resins, vinyl resins, Polyethylene resins and also in other resins can during the mixing masses that after the process according to the invention have been produced, are incorporated, and these are thereby Resins made fungus-proof. Mineral and synthetic waxes and fats with low and high melting points are made fungus-proof by dissolving or dispersing masses according to the invention in them.

The water-insoluble metal salts of oxyquinolines can be alkaline earth, heavy metal, aluminum, tin or Be beryllium salts in which the hydroxyl group converted into salt form is in any position in the benzene nucleus or nitrogen ring of the ChinoKnrest

909 770/429

located. It can also use salts of oxyquinolines with multiple hydroxyl groups can be used. Examples of these salts are calcium, barium, magnesium, Beryllium, lead, mercury, manganese, cobalt, nickel, iron, copper, cadmium, silver, Thallium, tin, zinc and aluminum salts of 2-oxyquinoline, 4-methyl-2-oxyquinoline, 4-oxyquinoline, 2-methyl-4-oxyquinoline, 5-oxyquinoline, 6-oxyquinoline, 7-oxyquinoline and 8-oxyquinoline.

The preferred products of the invention The products are made by reacting a water-insoluble soap with a process Phenol and a heavy metal salt, in particular a copper salt, of an 8-oxyquinoline are formed, z. B. with the copper salts of 8-oxyquinoline, S ^ -Dichloro-S-oxyquinoline and 5,7-dibromo-8-oxyquinoline.

Of the usable, water-insoluble metal salts of Oxyquinoline, the copper salt of 8-Oxyquinoline is preferred because it is commercially available is and easily with a water-insoluble soap and a phenol to masses with high fungicides and / or fungistatic properties reacts

The metal soaps used as the reactants are metal or water-insoluble soaps a mixture of metals and a soap-forming carboxylic acid or a mixture of such acids. The soaps of nickel, calcium, barium, magnesium, mercury, lead, cadmium, silver, thallium, Manganese, cobalt, iron, copper, tin or aluminum can be used. Preferred are the Copper, nickel and zinc soaps.

The soap-forming acids used to form the suitable metallic soaps include: caproic acid, Caprylic acid, capric acid, ethylhexanecarboxylic acid, lauric acid, myristic acid, palmitic acid, Stearic acid, oleic acid, linoleic acid, linolenic acid, palmitoleic acid, Melissic acid, oxystearic acid, ricinoleic acid and similar carboxylic acids and mixtures thereof. The preferred soap-forming acids are saturated and unsaturated higher aliphatic carboxylic acids with 6 to 18 carbon atoms and resin acids. Other suitable acids are the mixed ones higher fatty acids, especially those from animal or vegetable sources, e.g. B. from sardines and others Fish oils, made from lard, coconut oil, sesame oil, soybean oil, tung oil, corn oil or from partially or fully hydrogenated Derivatives of such oils, also from carnauba, spermaceti, bees, candelilla and similar waxes, obtained fatty acids, and the aliphatic ones obtained from petroleum or other hydrocarbons Carboxylic acids and naphthenic acids, tall oil fatty acids and hydroaromatic acids such as abietic acid.

The soaps and soap-forming acids mentioned do not only occur with the water-insoluble metal salt of the oxyquinoline and the phenol in reaction, but also support this reaction in that they serve as the reaction medium in which the reaction can conveniently be carried out. An essential one molar excess of metallic soap or metallic soap-forming acid, if the soap in the reaction is self-made, therefore does not represent a waste of this material.

Examples of such phenolic compounds are phenol, octylphenols, nonylphenols, o-amylphenol, p-cresol, o-cresol, m-cresol, p-chloro-m-cresol, tert. Butylm-cresol, p-nitrophenol, salicylaldehyde, salicylamide, o-cyclohexylphenol, resorcinol, pyrogallol, 2,4-chlorophenol, Pentachlorophenol,. Picric acid, thymol (5-methyl-2-isopropylphenol), 2,3,4,6-tetrachlorophenol, Tetrachlorohydroquinone, 6-tert-butyl-3-methylphenol, xylenols, chloroxylenols, 4-phenylphenol, 2,4,6 -tribromophenol, p-tolylphenol, xylylphenols, Salicylic acid phenyl ester, p-oxypropiophenone, salicylic acid methyl ester, 2,2 '- oxy - 5,5' - dichloro - diphenylmethane (= bis (5-chloro-2-oxyphenyl) methane) and any mixtures of these substances.

The following are illustrative examples of the process for preparing the reaction products of the invention. In each case, the reaction was carried out in a Pyrex glass reaction vessel with constant stirring the respondent carried out. But it can also be stored in a stainless steel reaction vessel Steel or other corrosion-resistant materials. The term "part" in the examples means "Part by weight".

example 1

The nickel salt of 2-ethylhexanecarboxylic acid was obtained by mixing 100 parts of 2-ethylhexanecarboxylic acid made with 60 parts of nickel acetate. This mixture was stirred and heated to 210 ° C until all acetic acid had evaporated. 100 parts of nonylphenol were then stirred into the solution. The addition of the phenol cooled the solution to 121 ° C. Then 58 parts of the copper salt of 8-oxyquinoline were taking Stirring added and the mixture heated to 171 ° C. A clear solution was obtained. 1 part of the obtained reaction product was diluted with 1 part of xylene. 1 part of the xylene solution was mixed with 19 parts light petroleum distillate diluted.

The resulting solution was used to treat tent canvas in the following manner. template 282 g of army tent canvas was cut into pieces of 25.5-76 cm, and the pieces were thoroughly washed, rinsed and dried. A piece was made with the diluted solution at room temperature soaked and then passed through a wringer to remove the excess impregnating solution remove. Approximately 50% wet weight gain was obtained so the fabric was about Contained 1.25% of the reaction product. The impregnated fabric was then kept at room temperature Air-dried for 24 hours to achieve almost complete removal of the solvent.

The treated tissue was in for 24 hours

leached out in running water and then horizontally in a well-composted soil about 1.5 cm deep buried under the surface. A control piece made from the same canvas but not treated with the Impregnation solution was buried in the same soil in the same way. Both pieces of tissue were made Leave in the soil for 28 days, during which time the soil temperature to about 21 ° C and the Moisture content was kept between 30 and 50%.

After these 28 days, both pieces of canvas were removed. The treated piece was washed to remove soil particles and air dried at room temperature. This piece retained its original appearance, showed no noticeable decrease in tensile strength and no other unfavorable or bad effects from storage in the ground. Against it the untreated piece was completely destroyed and disintegrated into many small soiled fragments.

Example 2

100 parts of 2-ethylhexanecarboxylic acid were mixed with 60 parts of nickel acetate, stirred and on

1 079 Ö40

Heated to 216 ° C until all acetic acid had evaporated. 100 parts of thymol (S-methyl ^ -isopropylphenol) were stirred into the mixture. The addition of the thymol lowered the temperature to about 121 ° C. Then 58 parts of copper salt of 8-oxyquinoline was added and the temperature of the mixture was raised increased to 171 ° C with stirring. A clear solution was obtained. 1 part of this solution was with 1 part benzene diluted. 1 part of this benzene solution was diluted with 19 parts of light mineral oil distillate.

A canvas pattern similar to that of Example 1 was impregnated with the diluted solution and then further treated and buried in the ground together with a control piece, exactly as in the example 1 described.

The treated specimen showed no noticeable attack by microorganisms while the control piece was completely destroyed.

20th

Example 3

100 parts of 2-ethylhexanecarboxylic acid were mixed with 60 parts of nickel acetate, the solution was stirred and heated to 216 ° C until all acetic acid had evaporated. 100 parts of mono-tert-butylmetacresol were stirred into the mixture, which lowered the temperature to 121 ° C. Then were Add 58 parts of the copper salt of 8-oxyquinoline to the mixture stirred in and the temperature increased to 171 ° C. A clear solution resulted. 1 part of the solution was diluted with 1 part of toluene. 1 part of this toluene solution was mixed with 19 parts of light mineral oil distillate diluted.

A canvas pattern similar to that of Example 1 was impregnated with the diluted solution and then further treated and buried in the ground, together with a control piece, exactly as in the example 1 described.

The treated test piece showed no noticeable attack by microorganisms, while the control piece was completely destroyed.

The reaction products of Examples 1 to 3 in the form of the solutions described were applied individually to wooden samples of about 2.5 x 7.5 cm and pieces of leather about 5 x 5 cm by suction under vacuum for 20 minutes and drying for 6 hours. The treated samples and untreated control samples of the same dimensions were placed on a sterile agar medium with a _pH value of 5.5, which was used as a substrate in petri dishes. Each treated sample and a control sample were placed in a different petri dish. The samples in all dishes were sprayed with a mushroom suspension of the following organisms and incubated at 30 ° C for 14 days:

Chaetomium globosum,
Penicillium citrinum,
Aspergillus niger,
Aspergillus terreus,

Trichoderma virida, Aspergillus flavus.

At the end of the test period it was found that the fungi were on the whole surface of the untreated Leather and wood control samples grew, but no growth on the treated leather and wood samples had taken place.

While in the above examples the water-insoluble soap was produced in the reaction vessel itself, it can also be made beforehand.

The reaction products according to the invention can also be incorporated directly into resins, fats and waxes will. A better distribution of the reaction products in such masses is obtained if the reaction products dissolved or dispersed in a suitable carrier.

The compositions obtainable by the process according to the invention not only prevent development of fungal organisms, but can also kill existing fungi on contact. Fabrics, such as textiles, Leather, wood and resins treated with compositions according to the invention are practically nonexistent sensitive to animal life in the ground and resist attack by bacteria and insects. The products of the process of the invention present themselves as insecticides in either dry or liquid form Form and as a means for the prevention and control of plant diseases and also against such Diseases, such as rot, which attack parts of plants under the ground.

Claims (3)

Patent claims: 1. Process for the production of fungicider and / or ungistatic masses by reaction of mixtures containing, in addition to a third component, water-insoluble metal salts of oxyquinolines and contain water-insoluble metal salts of carboxylic acids, characterized in that water-insoluble Metal salts of oxyquinolines with water-insoluble metal salts of aliphatic carboxylic acids, Naphthenic acids or hydroaromatic carboxylic acids, especially soap-forming ones Carboxylic acids, and with oxybenzene compounds of the general formula OH are reacted, wherein X is a hydrogen, chlorine or bromine atom or a hydroxyl, formyl or nitro group or an alkyl, aryl, alkaryl or aralkyl radical or a carbaminyl (H ₂ N- CO-) or carboxyl, carbalkoxy or a carbo-aryloxy group or an alkyloxy or aryloxy radical, η is an integer from 1 to 5, and, if η is greater than 1, the atoms, groups or radicals represented by X can be identical or different. 2. The method according to claim 1, characterized in that the metal salts of oxyquinolines, in particular of 8-oxyquinoline, aluminum salts or heavy metal salts, such as copper or tin salts, can be used. 3. The method according to claim 1 and 2, characterized in that the metal salt of a carboxylic acid, especially the 2-EthyHiexancarboxylic acid, the nickel salt is used. Considered publications:
U.S. Patent Nos. 2,561,379, 2,561,380. © SK 770/429 4.6 &