JPS6241482B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an agricultural and industrial bactericidal algaecide characterized by containing alkylenethiuram sulfide as an active ingredient. The object of the present invention is to provide a novel bactericidal algaecide for agricultural and industrial use that does not leave any harmful effects on useful organisms. Alkylene bisdithiocarbamate compounds have been known to have bactericidal and insecticidal effects, but generally when there is an alkylene group having two or more carbon atoms between two nitrogen atoms, that is, when the alkylene group is upgraded, It is generally believed that the effect of alkyl substituents on either or both of the two nitrogen atoms is reduced. However, it has been found that the presence of hydroxyalkyl groups has a significant effect. The present invention will be explained in detail below. The present invention is based on the general formula [However, X represents a lower alkylene group or -( _C2H4NH ) _{-oC2H4- group} (however, n _represents 1 or ₂ ), and Y and Y' represent hydrogen or a hydroxy lower alkyl group ( (However, this excludes the case where Y and Y' both represent hydrogen.), and p represents an integer of 1 to 4. ] Provided is an agricultural and industrial bactericidal algaecide containing thiuram sulfide as an active ingredient. The method for producing the active ingredient of the present invention is the general formula (X, Y, and Y' are the same as above, and M and M' represent soluble salt-forming salt parts.) If an aqueous solution of polydithiocarbamic acid shown in The disulfide is obtained and then the disulfide is treated with alcoholic KCN to obtain the alkylenethiuram monosulfide. Furthermore, alkylenethiuram polysulfide can be obtained by treating an aqueous solution of a soluble polydithiocarbamic acid salt represented by the above general formula with sulfur chloride. This will be explained in more detail. The compound used as an active ingredient in the drug of the present invention is generally prepared from polyamine, carbon disulfide, ammonia or caustic soda, or the like. A soluble salt such as diammonium or disodium polydithiocarbamate is added to nitrous acid, hydrogen peroxide,
When oxidized with chlorine, bromine, iodine, bleached powder (calcium hypochlorite), sodium hypochlorite, etc., or in some cases with air, a yellowish-white to white insoluble precipitate is produced in good yield. By separating and drying and pulverizing this, a white fine powder of thiuram disulfide, which is used as an active ingredient in the present invention, is obtained. Dilute alcoholic to this thiuram disulfide
When KCN is added and heated, thiuram monosulfide is produced. Thiuram polysulfide can also be obtained by treating the polydithiocarbamic acid salt solution with sulfur chloride. The procedure is to gradually add sulfur chloride to an aqueous solution of polydithiocarbamate while stirring. In this case, it is preferable to cool it from the outside.
Then, a yellow inert precipitate is produced in good yield. This compound features a composition of thiuram polysulfide. In this case, not only sodium salts and ammonium salts but also any salts may be used as long as they are water-soluble. The specific examples described above are merely used for illustrative purposes and are not intended to limit the scope of the invention. As the simplest example, when N-(2-hydroxyethyl)-ethylenebisdithiocarbamate is used, the structures of thiuram monosulfide, thiuram disulfide, and thiuram trisulfide are shown. These thiuram monosulfide and thiuram polysulfide are new compounds, and their bactericidal and algicidal activity is significantly stronger than that of Zineb, which has been conventionally used as a fungicide. When the composition of the present invention is used for agricultural and horticultural purposes, it generally exhibits high pest control activity without phytotoxicity. The sulfide of the present invention has hydrophilic properties, unlike conventionally known ethylenethiuram monosulfide, due to the hydrophilic hydroxy group in its chemical structure, and is therefore more water-soluble than conventional ethylenethiuram sulfide. is high. It also has surface activity, and a spray solution containing it has good wetting and spreading. The suspension state of the part that is not soluble in water but suspended in water is much better than that of conventional products.
This property has a great influence on the action and activity, and shows higher biological activity than known products that do not contain hydroxyl groups. For use, the product can be applied directly as is, or by using suitable solid carriers, liquid carriers, emulsifying dispersants, etc., according to pesticide formulation methods commonly known in the art. granules,
It can be applied in any form such as powder, emulsifier, wettable powder, flow dust, tablet, oil, and atomizer. Examples of these carriers include clay, kaolin, bentonite, acid clay, diatomaceous earth, calcium carbonate, white carbon, nitrocellulose, starch, gum arabic, benzene, xylene, alcohol, acetone, kerosene, dimethylformamide, freon, and the like. Can be done. In addition, adjuvants commonly used in formulations,
For example, soap, sulfuric acid esters of higher alcohols, alkyl sulfonates, alkylaryl sulfonates, quaternary ammonium salts, polyalkylene oxides, etc. may be appropriately blended as surfactants such as spreading agents, emulsifiers, and dispersants. Can be done.
Further, stabilizers such as hexamethylenetetramine, paraformaldehyde, urea, N·N'-dimethylol urea, diaminotoluene, etc. may be added. Furthermore, preparations made by adding a specific gravity regulator to the composition of the present invention to form emulsifiers or oils are effective as aerial spraying agents by aircraft. It is also very easy and effective to pulverize the product of the present invention together with an auxiliary agent such as white carbon to reduce the average particle size and the tentative specific gravity, and use it as a so-called flow dust agent. Furthermore, since the products of the present invention are chemically stable, they can be blended with other active ingredients, such as sterilizing, insecticidal, acaricidal, herbicidal, and plant growth regulators. Furthermore, when used for industrial purposes, it is possible to prevent contamination and damage caused by mold and other microorganisms that occur in the paint film, and also to prevent contamination by slime, algae, etc. that occur in cooling water. Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. Production Example 1 80 g of carbon disulfide and 100 g of water were put into a three-necked flask, stirred vigorously, and 52 g of N-(2-hydroxyethyl)ethylenediamine was added dropwise at 30 to 40° C. The dropwise addition time was 1 hour. After that, 84 g of 50% caustic soda aqueous solution was gradually added dropwise, and for another 1 hour 38
Heat and stir at ~40°C. The dithiocarbamic acid content of the disodium salt was analyzed using a carbon disulfide quantitative method using acid decomposition, and the reaction rate between the amine and carbon disulfide was determined to be 97% based on the amine. The content of the above disodium salt aqueous solution as _CS2 is 12-15%
Adjust so that Dissolve a small amount of methanol and 1 mole of sodium nitrite in this solution to make 30%
Pour into a four-necked flask and stir to cool. 10~15℃
Keep it. Two moles of hydrochloric acid and the remaining disodium salt aqueous solution are added separately to this. At this time, cool and maintain the temperature at 10-15℃. Further, unreacted dithiocarbamate is always allowed to remain in the reaction vessel. A large amount of yellow-orange precipitate is formed. This was separated and dried to obtain N-(2-hydroxyethyl)ethylenethiuram disulfide as a yellow-orange solid. The total yield was 90%. Production Example 2 N-(2-hydroxyethyl)ethylenebisdithiocarbamic acid disodium salt obtained in the same manner as in Production Example 1 is adjusted to have a concentration of 8 to 10% as _CS2 . To this, an excess of aqueous caustic soda solution is added and while cooling to 5 to 10°C, chlorine gas is passed over the liquid surface. Chlorine gas is passed until a yellow precipitate is formed but no more yellow precipitate is observed. Separate the product while keeping it alkaline. The yield is around 90%, and N-(2-hydroxyethyl) is a yellow-orange solid.
Ethylenethiuram disulfide was obtained. This reaction can be carried out in the same manner with bromine or iodine (iodine-iodine potassium salt). Production Example 3 The same success can be achieved by replacing sodium N-(2-hydroxyethyl)ethylenebisdithiocarbamate as in Production Example 1 with calcium hypochloride or hydrogen peroxide. Production Example 4 600 g of a 50% sodium N-(2-hydroxyethyl)ethylenebisdithiocarbamate aqueous solution is cooled to 5 to 10°C while stirring. Chlorine gas is introduced above the liquid surface at 5 to 10°C. N-(2-
A precipitate of hydroxyethyl) ethylenethiuram disulfide forms. Next, when no precipitated product is observed, the product is filtered, washed with water and dried. Production Example 5 26g of N-(2-hydroxyethyl)ethylenethiuram disulfide obtained in the above example
Add to 200ml of 20% ethanol and stir while stirring.
7 g of potassium cyanide dissolved in 50 ml of 20% ethanol aqueous solution was dropped. After the addition, the mixture was stirred under reflux for 3 hours. The ethanol was collected and filtered after cooling to room temperature.
Washed with water and dried. Yellow N-(2-hydroxyethyl)ethylenethiuram monosulfide was obtained. Production Example 6 N-(2-
313 g of a 48% aqueous solution of sodium ethylene bisdithiocarbamate (hydroxyethyl) as CS ₂ concentration
Adjust to 10-15%. To this, 70 g of sulfur chloride was gradually added dropwise while stirring while maintaining the temperature at 5 to 10°C. The precipitate was filtered, washed with water, and then dried. Yellow solid N
-(2-hydroxyethyl)ethylenethiuram sulfide was obtained. The monosulfides and polysulfides obtained according to the above examples are as follows.

[Table] Example 1 A diluted solution of a test chemical at a predetermined concentration was sprayed using a small power sprayer when the 7th true leaf of a tomato (cultivar Kagoshima Fukuju) was grown in a Firelon house. (Adding a spreading agent). Two days after spraying, inoculation was carried out by uniformly spraying a tomato Phytophthora spore suspension. The survey was conducted 10 days after vaccination.
On day one, the number of affected leaflets was counted for 5 leaves per plant and 7 leaflets per compound leaf (ranked as 0, 1, or 2). Test drug active ingredient concentration: 75% hydrating powder.

[Table] Example 2 A diluted solution of a test chemical at a predetermined concentration was sprayed using a small glass sprayer when the third true leaf of a cucumber (variety Tokiwa No. 3) grown in a Firelon house was set.
(Adding a spreading agent). Two days after spraying, a suspension of spores of the cucumber scoliosis fungus was spray inoculated and placed in a greenhouse with a humidity of 90% or more to encourage the onset of infection. On the 10th day after spraying, the top two leaves developed at the time of spraying were investigated according to disease severity (grades 0 to 4). Test drug active ingredient concentration: 75% hydrating powder. Regarding drug damage, (-) indicates no drug damage, (±) indicates almost no drug damage, (+) indicates drug damage, and (++) significantly drug damage.

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[Table] Example 3 A paint containing the fine powder of the product of the present invention was applied to an iron test piece, and a bactericidal activity test was conducted on the film. Using Amber Rack 292G manufactured by Rohm and Haas, it was mixed with 2 parts by weight, 1 part by weight of titanium oxide, and 1 part by weight of Solvesso150.
This paint was blended with 0.65 and completely miscible using a roller mill, and was uniformly mixed with the agent of the present invention (400 mesh or less) at a ratio of 95 and 5 by weight to JIS-G- 3303 on a soft iron test piece using a 0.005mm doctor plate and heat treated. Bacillus Subtilis is used as the test bacterium. The growth inhibition phenomenon of Bacillus subtilis on the paint film was measured by counting the number of colonies.

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[Table] Example 4 Fresh water containing mainly diatoms was placed in a beaker 1, the chemical of the present invention was added thereto, and the beaker was gently stirred and left for one week. All the algae in the beaker turned white and died. Also, Flavobacterium, which causes slime
The drug of the present invention was tested against lactis and Flavobacterium peregrinum. One platinum loopful of each bacterial suspension was inoculated into Waxmann's medium supplemented with the drug of the present invention, and cultured at 30°C for 3 days. All of the drugs of the present invention almost inhibited growth.

Claims (1)

[Claims] 1. General formula [However, X represents a lower alkylene group or -( _C2H4NH ) _-C2H4- group ( _however , n represents 1 or 2), and _Y and Y' represent hydrogen or monohydroxy lower It represents an alkyl group (except when Y and Y' simultaneously represent hydrogen), and p represents an integer of 1 to 4. ] An agricultural and industrial bactericidal algaecide characterized by containing thiuram sulfide as an active ingredient.