JPS6411605B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an agricultural and industrial microbicide, and more particularly, the present invention relates to a microbicide for agricultural and industrial use, and more specifically, [However, X represents a lower alkylene group or a polylower alkylene polyamine residue, and Y and Y' represent hydrogen or a hydroxy lower alkyl group (however, Y and
Except when Y′ also represents hydrogen. ), M
indicates an alkali metal. ] A soluble metal salt selected from zinc, manganese, iron, and copper is added to a mixed solution of a salt represented by the above general formula and an amine, or a mixed solution of a salt represented by the above general formula, an amine, and a lower aliphatic aldehyde. This invention relates to an agricultural and industrial microbicide whose active ingredient is a product obtained by an additive reaction. Alkylene bisdithiocarbamate compounds have long been known to have bactericidal and insecticidal effects, but their effectiveness is generally said to decrease when the alkylene group that has two or more carbon atoms between two nitrogen atoms is upgraded. ing. However, when a hydroxyalkyl group is present on the nitrogen atom,
It was found that this method had a remarkable effect, and based on this, the present invention was completed. 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 a polylower alkylene polyamine residue, and Y and Y' represent hydrogen or a hydroxy lower alkyl group (however, Y and
Except when Y′ also represents hydrogen. ), M
indicates an alkali metal. ] A soluble metal salt selected from zinc, manganese, iron, and copper is added to a mixed solution of a salt represented by the above general formula and an amine, or a mixed solution of a salt represented by the above general formula, an amine, and a lower aliphatic aldehyde. This invention relates to an agricultural and industrial microbicide whose active ingredient is a product obtained by an additive reaction. The amines that can be used as raw materials in the present invention include general monoamines, polyamines or salts thereof, compounds of quaternary ammonium salts, and other ammonia and inorganic ammonium salts. Representative examples of monoamines include monoalkylamines such as monomethylamine monoethylamine, isopropylamine, Sec-butylamine laurylamine, 2-ethylhexylamine, monoethanolamine, methoxypropylamine, and cyclohexylamine; aniline, chloroaniline, Monoarylamines such as dichloroaniline, aminomesitylene, xylidine, toluidine, and anisidine; monoaralkylamines such as benzylamine, chlorobenzylamine, dichlorobenzylamine, P-brombenzylamine, and phenechelamine; and the like. Also, dialkylamines such as dimethylamine, diethylamine, didodecylamine, diethanolamine, di(2-methoxyethyl)amine, and methylethanolamine; diarylamines such as diphenylamine and di(P-nitrophenyl)amine; methylaniline, ethylaniline, P-methoxyphenylmethylamine,
Included are arylalkylamines such as P-triethylamine. Also trimethylamine, triethylamine, tridecylamine, triethanolamine, N,N-dimethylethanolamine,
Included are N,N-dibutylethanolamine, triphenylamine, dimethylbenzylamine, diphenylmethylamine, diethylphenylamine dimethylaniline, and the like. Representative examples of heterocyclic amines include morpholine, piperidine, pyrrolidine, aminopyridine,
Includes aminothiazole, etc. Representative examples of polyamines include ethylenediamine, propylenediamine, butylenediamine, N-methylethylenediamine, N-(2-hydroxyethyl)ethylenediamine, and N-(2-hydroxypropyl).
Ethylenediamine, piperazine, phenylenediamine, xylylenediamine, dimethylaminoethylamine, tetramethylethylenediamine, N,
Included are N'-diphenylethylenediamine, N-phenylethylenediamine, N,N'-diethanolethylenediamine, N-ethanolethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and the like. Representative examples of quaternary ammonium salts include tetramethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethanolammonium hydroxide, benzyltrimethylammonium hydroxide, dodecylbenzyldimethylammonium hydroxide, tetramethylammonium chloride, tetrabutylammonium chloride, Included are benzyltrimethylammonium chloride, dodecylbenzyldimethylammonium chloride, dodecylbenzyldimethylammonium chloride, tetradecylbenzylmethylammonium chloride, hexadecylbenzyldimethylammonium chloride, octadecylbenzyldimethylammonium chloride, benzethonium chloride, and the like. The amounts of these amines to be used will be explained below. Further, lower aliphatic aldehydes used in the present invention include formaldehyde, acetaldehyde, halogenated acetaldehyde,
Examples include cycloacetaldehyde and chloral. The lower aliphatic aldehyde is 1:1 for the N-substituted alkylene bisdithiocarbamate of the present invention.
It is used in a molar ratio of 0.5 to 3, preferably 1:1 to 2. The product of the present invention is prepared by dissolving the above-mentioned alkali polydithiocarbamate salt and amines and, if necessary, an aliphatic aldehyde in a solvent such as water or alcohol, and then preparing a water-soluble compound selected from zinc, manganese, iron, and copper. It is obtained by adding and reacting an aqueous solution of a metal salt. It is generally carried out in an aqueous solution, but methanol,
Solvents such as ethanol and isopropanol can also be used. When the water solubility of the amine is limited, it is desirable to dissolve it in a suitable solvent such as an alcoholic solvent and add it to the polydithiocarbamate. Further, it is preferable to form the polydithiocarbamate-amine mixture into a solution before adding the metal salt.
In some cases, this reaction may be performed using dimethyl sulfoxide,
It may be desirable to carry out the reaction in a solvent such as dimethylformamide and then add a sufficient amount of water to precipitate the polydithiocarbamate metal salt complexed with amines. The reaction proceeds satisfactorily at temperatures in the range 0-50°C. It is particularly good to keep the temperature of the reactant solution within the range 10-30°C. Although higher temperatures can be used, at higher temperatures the polydithiocarbamate solution is susceptible to decomposition and the yield of the desired product is reduced. To obtain the products of the invention, the molar ratio of metal moieties to polydithiocarbamate moieties is from 1:0.5 to
2 is preferred. When metal salts are used as a mixture, the molar ratios of the combined metal salts may be the same. An additional excess of metal salt relative to the polydithiocarbamate moieties can be used, and this excess amount is governed by economic and other considerations. Excesses of metal salts such as copper sulfate can be used. Further, the molar ratio of the amine moiety to the polydithiocarbamic acid moiety is 1:0.01 to 4,
Preferably it is 1:1-2. The concentration of the combined polydithiocarbamate and amine solution is limited only by the solubility of these reactants in the reaction solvent. Satisfactory results were obtained when the solids concentration was varied from 2% to 35%. Completion of the reaction is indicated by the formation of a precipitate. This precipitate can be recovered from the reaction solution by means well known to those skilled in the art. A typical example is drying under vacuum at high temperatures. Yields of 90-100% of theory are usually obtained in this way. In addition to filtration, methods such as centrifugation, sedimentation, and pouring out the supernatant can also be easily used. The soluble metal salt used in the metal part is selected from the group consisting of zinc, manganese, iron and copper. Specifically, zinc chloride, zinc sulfate, zinc nitrate, zinc acetate,
These include manganous chloride, manganese sulfate, manganese nitrate, manganese acetate, cupric chloride, copper sulfate, copper nitrate, copper acetate, ferric chloride, iron sulfate, iron nitrate, iron acetate, and the like. The specific examples used in the above description of the polydithiocarbamic acid moiety, the amine moiety, and the metal moiety are merely used for illustrative purposes and are not intended to limit the present invention. Also, many modifications and changes that are obvious to those skilled in the art can be used within the general concept of the manufacturing method of the invention. For example, certain amine hydrochlorides are liquids at room temperature. When such amine hydrochlorides are used, they may be used as reaction medium either by themselves in excess or with small amounts of other solvents to enhance the necessary solubility of the other reactants. May be used for It goes without saying that all such modifications are included within the scope of the present invention. The product of the present invention has significantly stronger bactericidal activity than Zineb or Ziram agents, which are used as conventional bactericidal agents. The products of the invention are stable at room temperature. However, it tends to gradually decompose at high temperatures or during long-term storage, but by adding a stabilizer it is possible to obtain a product (drug) with further improved stability. Stabilizers may be added during production or during formulation. Stabilizers include hexamethylenetetramine, paraformaldehyde, 0-tocurbiguanide, diphenylguanidine, diaminotoluene, 1,8
-3,6-diedomethylene-1,3,6,8-
Tetra-azacyclodecane, N,N'-dimethylolurea, 1,3,5-tris(cyanomethyl)
Examples include hexahydrotriazidi, urea, N-methylurea, N,N'-dimethylurea and the like. When the products of the present invention are used for agricultural and horticultural purposes, they generally exhibit high pest control activity without phytotoxicity. For use, the product can be applied directly as is, or it can be granulated using suitable solid carriers, liquid carriers, emulsifying dispersants, etc., according to agricultural formulation methods commonly known in the art. agent,
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, and freon. be able to. In addition, adjuvants commonly used in formulations, such as surfactants such as spreading agents, emulsifiers, and dispersants, include soaps, sulfuric acid esters of higher alcohols, alkyl sulfonates, alkylaryl sulfonates, and quaternary ammonium salts. and polyalkylene oxide, etc. can be appropriately blended. Further, preparations made by adding a specific gravity regulator to the product of the present invention to form an emulsifier or an oil agent are effective as aerial spraying agents by aircraft. The product of the present invention is finely pulverized together with an adjuvant such as white carbon to reduce the average particle size and the temporary specific gravity of the so-called flow dust agent.
It is also extremely easy and effective to use it as 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 34 g of 45% N-(2-hydroxyethyl)ethylenebisdithiocarbamate aqueous solution, 5.6 g of 40% dimethylamine aqueous solution and 200 ml of water were added and stirred to form a homogeneous solution. Add this to 50% zinc chloride aqueous solution
13.6g was gradually added dropwise at room temperature. After the dropwise addition, the mixture was stirred at room temperature for 2 hours, and the resulting precipitate was filtered off under suction and washed with water. It was further dried under reduced pressure at 40-50°C/20mmHg to obtain a pale yellow solid product. Let product number be 1. Production Example 2 11.3 g of a 40% dimethylamine aqueous solution was diluted with 100 ml of water, and the pH was adjusted to 7 by adding about 10 g of concentrated hydrochloric acid. Next, 34 g of a 45% aqueous solution of sodium N-(2-hydroxyethyl)ethylenebisdithiocarbamate was added to this solution to form a homogeneous solution. 47 in this solution
% zinc chloride aqueous solution is added dropwise over 30 minutes. After dropping, stir at room temperature for 1 hour. The generated precipitate was filtered, washed with water, and dried under reduced pressure at 40-50°C/20 mmHg to obtain a pale yellow solid product. Let product number be 16. Production Example 3 23.8 g of a 35% methanol solution of trimethylbenzylammonium hydroxide was adjusted to pH 7 with a 42% aqueous solution of fluoroboric acid diluted with 100 ml of water. To this solution was added 16.7 g of a 45% aqueous solution of sodium N-(2-hydroxyethyl)ethylenebisdithiocarbamate while stirring at room temperature. An aqueous solution prepared by dissolving 3.0 g of manganese acetate tetrahydrate in 50 ml of water is added dropwise to this mixed solution over 20 minutes at room temperature. The generated precipitate is filtered and washed with water at 40-50℃/20mmHg.
The mixture was dried under reduced pressure to obtain a yellow solid product.
Let product number be 17. The complex polydithiocarbamate metal salt of amines obtained according to the above example is as follows. The following polydithiocarbamic acids were used. Symbol Polydithiocarbamate (A) (a) Sodium N-(2-hydroxyethyl)ethylenebisdithiocarbamate (b) Sodium N-(2-hydroxypropyl)ethylenebisdithiocarbamate (c) Sodium N-(2-hydroxypropyl)propylenebisdithiocarbamate (d) Sodium N-(2-hydroxy-1,2-dimethylethyl)ethylenebisdithiocarbamate (e) N-(3-hydroxypropyl) Sodium ethylenebisdithiocarbamate (f) N,N'-di(2-hydroxyethyl)
Sodium ethylene bisdithiocarbamate (g) Sodium N-(2-hydroxypropyl)diethylenetriaminebisdithiocarbamate (h)Sodium N-(2-hydroxypropyl)triethylenetetraminebisdithiocarbamate As the amine part: The following was used. Symbols Amines (B) (a) Monomethyl (b) Aniline (c) Laurylamine (d) Benzylamine (e) Dimethylamine (h) Diethanolamine (g) Trimethylamine (h) N,N-dibutylethanolamine (li) ) Moripholine (N) Ethylenediamine (L) Phenylenediamine (E) N-(2-hydroxyethyl)ethylenediamine (W) Diethylenetriamine (F) Tetramethylammonium hydroxide (Y) Benzyltrimethylammonium hydroxide (T) Ammonium chloride A mixed solution selected from the above polydithiocarbamic acid (A) and amines (B) was treated with one type of water-soluble metal salt (c) selected from zinc, manganese, iron, and copper.

[Table] Production example 4 34g of 45% N-(2-hydroxyethyl)ethylenebisdithiocarbamate sodium aqueous solution at 50°C
37% formaldehyde aqueous solution while stirring
After adding 4.5 g and reacting for 15 minutes, the mixture was cooled to 30°C. Additionally, 3.8g of 40% monomethylamine aqueous solution
The mixture was added and stirred to obtain a homogeneous solution. While stirring at 30°C, 13.6 g of a 50% aqueous zinc chloride solution was gradually added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 2 hours, and the resulting precipitate was filtered off under suction and washed with water. The product is 40-50
The product was dried under reduced pressure at °C/10 mmHg to obtain a pale yellow solid product. Product number 23. Example 1 A diluted solution of a test chemical at a predetermined concentration was sprayed using a small power sprayer when the seven true leaves of a tomato (cultivar Kago Fukuju) grown in a Firelon house were set. (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 the second day, the number of affected leaflets was counted for 5 leaves per plant and 7 leaflets per compound leaf (classified as 0, 1, or 2) to calculate the control value. 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 the degree of disease (grades 0 to 4). Test drug active ingredient concentration, 75% hydrating powder.

[Table] Example 3 Flavobacterium lactis that causes slime
and Flavobacterium peregrinum were tested. Waxmann medium (10ml) containing the drug of the present invention
One platinum loopful of each bacterial suspension was inoculated onto a plate, cultured at 30°C for 3 days, and the presence or absence of bacterial growth was examined. The results are shown in the table below.

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Claims (1)

[Claims] 1. General formula [However, X represents a lower alkylene group or a polylower alkylene polyamine residue, and Y and Y ^- are
Represents hydrogen or a hydroxy lower alkyl group (excluding cases where Y and Y ^- simultaneously represent hydrogen),
M represents an alkali metal. An agricultural industry characterized by containing as an active ingredient a product obtained by adding and reacting a soluble metal salt selected from zinc, manganese, iron, and copper to a mixed solution of the salt shown in ] and amines. Microbicide for use. 2 General formula [However, X represents a lower alkylene group or a polylower alkylene polyamine residue, and Y and Y ^- are
Represents hydrogen or a hydroxy lower alkyl group (excluding cases where Y and Y ^- simultaneously represent hydrogen),
M represents an alkali metal. ] Salt shown in
Agricultural and industrial use characterized by containing as an active ingredient a product obtained by adding and reacting a soluble metal salt selected from zinc, manganese, iron and copper to a mixed solution of amines and lower aliphatic aldehydes. Microbicide.