JPH0134962B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is an industrial production method that has low toxicity to the human body and various useful organisms, prevents or suppresses the growth and proliferation of harmful organisms, and does not leave any harmful effects on the human body or useful organisms after the action. This invention relates to an agricultural and industrial microbicide that is easy to use. The present invention is based on the general formula [However, X represents a lower alkylene chain or a lower alkylene chain separated by at least one nitrogen atom, and Y or Y' represents hydrogen or a hydroxy lower alkyl group (provided that Y and
Except when Y′ also represents hydrogen. ). ] A water-soluble salt of bisdithiocarbamic acid and a water-soluble salt of lower alkylene bisdithiocarbamic acid, or a water-soluble salt of diethylenetriamine or triethylenetetramine bisdithiocarbamic acid, or the general formula (However, A and B represent hydrogen, a lower alkyl group, or an amino group.) Obtained by metathesis of a water-soluble salt of monodithiocarbamic acid with a water-soluble manganese salt or a water-soluble copper salt. The present invention relates to an agricultural and industrial microbicide characterized by containing as an active ingredient a dithiocarbamic acid mixed metal salt in which zinc or copper is complexed with a dithiocarbamic acid mixed single metal salt. When the metal salt of bisdithiocarbamic acid shown in (A) used as a raw material for the drug of the present invention is finely pulverized, it exhibits excellent biological activity, especially protective action as a drug. However, if the molecular weight is too large, its effect will be slowed down.
On the other hand, if the molecular weight is too low, it becomes water-soluble and may cause drug damage or be washed away and lose its protective effect. Therefore, a technique is needed to control the protective structure of hydroxypolydithiocarbamic acid, especially its molecular weight. One method for controlling the molecular weight of polymers is the method of forming an end group. Moreover, the same thing can be said about the metal salts of lower alkylene bisdithiocarbamic acids and the metal salts of polyethylene polyamine polydithiocarbamic acids as in the case of the above-mentioned polydithiocarbamic acids. Therefore, by adjusting the molar ratio of bisdithiocarbamic acid and lower alkylene bisdithiocarbamic acid or polyethylene polyamine polydithiocarbamic acid represented by the general formula, the concentration of the unterminated group can be adjusted and it can act freely. to obtain different metal salts.
Furthermore, if monodithiocarbamic acid represented by the general formula is used, this acts as an end group-forming group. Another characteristic of monodithiocarbamic acid is that it exhibits excellent biological activity, but it is also known to exhibit phytotoxic effects on plants, etc.; however, if monodithiocarbamyl group is used as an unterminated group, The objective is to demonstrate the effect of reducing drug-induced harmful effects. If a certain molar ratio of a water-soluble salt of bisdithiocarbamic acid and a soluble salt of monodithiocarbamic acid are metathesized in advance with a water-soluble metal salt in a solvent, the monovalent dithiocarbamic acid acts as an end-forming group, The polymerization of bisdithiocarbamate metal salts can be controlled, the molecular weight can be appropriately controlled, and metal salts with significantly increased biological activity can be obtained without increasing water solubility. In addition, the water-soluble salt of dithiocarbamic acid used in the present invention is a mixed solution of the corresponding amine, and a mixed dithiocarbamate is obtained by reacting it with carbon disulfide in a corresponding molar ratio in the presence of an alkali. This is metathesized with a water-soluble metal salt to obtain the metal salt that is the raw material of the present invention. The reaction solvent may generally be carried out in an aqueous solvent, and any solvent may be used as long as the reaction solute is dissolved therein. Specific examples include pyridine, methanol, ethanol, ipropanol, N-methyl-2-pyrrolidone, sulforane, dimethylformamide, dimethylacetamide, dimethylsulfoxide, dioxane, and tetrahydrofuran. The reaction is preferably carried out at a temperature in the range of 0 to 60°C. Specific examples of water-soluble metal salts used in metathesis include manganese chloride, manganese sulfate, manganese nitrate, manganese acetate, copper chloride, copper sulfate, copper nitrate, and the like or a mixture of different metal salts. Specific examples of bisdithiocarbamic acid represented by the general formula (A) include N-(2-hydroxyethyl)ethylenebisdithiocarbamic acid, N-hydroxymethylethylenebisdithiocarbamic acid, N-( 2-Hydroxyethyl)propylene bisdithiocarbamic acid, N-(2-hydroxypropyl)ethylenebisdithiocarbamic acid, N-
(3-hydroxypropyl)ethylenebisdithiocarbamate, N,N'-di(2-hydroxyethyl)ethylenebisdithiocarbamate, N,
N'-di(2-hydroxypropyl)ethylenebisdithiocarbamate, N-(2-hydroxypropyl)diethylenetriaminebisdithiocarbamate, N-(2-hydroxypropyl)triethylenetetraminebisdithiocarbamate, N ，
N'-di(2-hydroxypropyl)diethylenetriaminebisdithiocarbamic acid, N-hydroxyethylaminoethylethylenebisdithiocarbamic acid, N-hydroxymethylaminoethylpropylenebisdithiocarbamic acid, N,N'-di( Examples include, but are not limited to, hydroxyethylaminoethyl ethylenebisdithiocarbamic acid, N-hydroxymethylaminoethylethylenebisdithiocarbamic acid, and the like. Specific examples of lower alkylene bisdithiocarbamic acid or polyethylene polyamine dithiocarbamic acid include aliphatic bisdithiocarbamic acids such as ethylene bisdithiocarbamic acid, propylene bisdithiocarbamic acid, and butylene bisdithiocarbamic acid; Examples include diethylene bisdithiocarbamic acid, triethylenetetramine bisdithiocarbamic acid, and the like. Specific examples of monodithiocarbamic acid represented by general formula (B) include methyldithiocarbamic acid, ethyldithiocarbamic acid, propyldithiocarbamic acid, butyldithiocarbamic acid, and dimethyldithiocarbamic acid. acid, diethyldithiocarbamic acid, dipropyldithiocarbamic acid, dibutyldithiocarbamic acid, carbazic acid, and the like. If the reaction is completed by adding the heavy metal salt as a solid or an aqueous solution to a slurry in which the dithiocarbamic acid mixed metal salt thus prepared is suspended in a solution medium, particularly an aqueous medium, the drug of the present invention is obtained. .
Further, both may be added at the same time or vice versa. These reactions are preferably carried out at a temperature range of 0 to 60°C. The drug of the present invention thus produced contains an additive metal. That is, if the manufactured drug of the present invention is washed with water, dried, and analyzed, the metal will be detected. Additive metal salts include zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, zinc oxide, zinc phosphate, zinc hydroxide, copper chloride, copper sulfate,
Examples include mixtures of the same or different metal salts such as copper nitrate, copper acetate, copper hydroxide, copper phosphate, and the like. The metal salt of the present invention is obtained as a solid and is relatively stable at room temperature. When the drug of the present invention is used for agricultural and horticultural purposes, particularly for fruit trees and vegetables, it can be applied directly as it is, or it can be applied using a suitable solid carrier, liquid carrier, emulsifying dispersant, etc. according to commonly known formulation methods. , granules,
It can be applied in any dosage form such as a powder, emulsion, wettable powder, tablet, oil, flowable, flow dust, or atomized powder. It can also be used as a soil treatment agent. Examples of the carrier include clay, kaolin, bentonite, acid clay, diatomaceous earth, calcium carbonate, white carbon, and starch. In addition, adjuvants commonly used in formulations,
For example, a spreading agent, an emulsifier, a dispersing agent, a stabilizer, etc. can be added as appropriate. For example, surfactants such as soap, sulfuric esters of higher alcohols, alkyl sulfonates, alkylaryl sulfonates, quaternary ammonium salts, and polyalkylene oxides can be used as spreading agents and dispersants, and hexamethylene Tetramine,
Paraform, urea, N,N'-dimethylol urea,
Diaminotoluene and the like can be used as stabilizers.
Furthermore, since the metal salt of the present invention is chemically stable,
It can also be blended with other active ingredients, such as fungicides, insecticides, acaricides, herbicides, plant growth regulators, etc. When used for industrial purposes, it can be incorporated into paint films, etc. to prevent contamination and damage caused by mold and other microorganisms, and can also prevent contamination by slime, algae, etc. that occur in cooling water, etc. . The present invention will be explained below with reference to Examples. Production example 1 Put 80g of charcoal disulfide and 150g of water into a three-necked flask and stir vigorously to prepare N-(2-hydroxyethyl).
A mixed solution of 26 g of ethylenediamine and 17.6 g of an 85% aqueous ethylenediamine solution is added dropwise at 30 to 40°C. The dropping time was 1 hour. then caustic soda
Add 80g as a 50% aqueous solution and heat and stir at 38-40°C for 1 hour. The dithiocarbamic acid content of the mixed soda 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 96% based on the amine. The following operations are performed in a nitrogen stream. Equimolar amounts of this reaction solution and manganous chloride were reacted in a concentrated aqueous solution. The resulting precipitate was washed three times by decanting to give a slurry containing 30% product. To 400 g of this slurry was added and mixed a solution of 12 g of zinc nitrate hexahydrate dissolved in 25 g of water. This mixture for 1 hour25
After stirring at ~30°C, the mixture was filtered and washed with water. 40～
Dry at 50°C/20mmHg. Analysis value CS ₂ 50.92% Mn 18.51% Zn 2.10% Product number 1. Production Example 2 A mixed soda salt obtained in the same manner as in Example 1 was metathesized with an equivalent amount of cupric chloride aqueous solution, and the resulting precipitate was washed three times by tilting to obtain a slurry containing 30% of the product. . 25g to 400g of this slurry
A solution of 25 g of cupric chloride dihydrate dissolved in water was added dropwise and stirred. Heat this mixture at 25-30°C for 30 minutes.
After stirring, the mixture was filtered and washed with water. 40~50℃/
Dry at 20 mmHg. Analysis value CS ₂ 44.02% Cu 27.20% Product number 10. Production Example 3 Zinc oxide is added to a slurry of 100 g of metal salt obtained by double decomposition of a mixed water-soluble salt of anhydrous N-(2-hydroxyethyl)ethylenebisdithiocarbamic acid and ethylenebisdithiocarbamic acid with manganese chloride. 2g were mixed uniformly. This mixture was stirred for 30 minutes at room temperature, and then filtered and washed with water repeatedly. This is designated as product number 14. The following products were produced according to the above production example. The molar ratio of polydithiocarbamic acid (A) represented by the selected general formula (A) and a water-soluble salt of alkylene or polyalkylene polyamine bisdithiocarbamic acid (C) is 1:1 to 2:1. The metal salts were selected from manganese, zinc, iron and copper in suitable combinations and equivalent amounts. A water-soluble metal salt selected from zinc, manganese, iron, and copper was added to 400 g of a 30% slurry of these metal salts for treatment. The following polydithiocarbamates represented by general formula (A) were used. Shown by general formula (A)

[Table] Da

【table】

[Table] Production Example 4 45 g of 37% formaldehyde aqueous solution was added to 230 g of 28% sodium ethylene bisdithiocarbamate aqueous solution at 50°C with stirring, and after reacting for 20 minutes, 28% sodium ethylene bisdithiocarbamate aqueous solution was obtained. 230g was added to make a homogeneous solution. Equimolar amounts of this reaction mixture and manganous chloride were reacted in a concentrated aqueous solution. The resulting precipitate was washed by decanting to give a slurry containing 30% product. 400g of this slurry was dissolved in 25g of water.
12g of zinc nitrate hexahydrate solution was added and mixed.
After stirring this mixture for 1 hour at 25-30°C,
filtered and washed with water. This was dried under reduced pressure at 40-50°C/20mmHg. Let product number be 15. Analysis value CS ₂ 50.2% Mn 18.2% Zn 2.4% Production example 5 Carbon disulfide 80g, water 150g in a three-necked flask
was stirred vigorously, and a mixture of 26 g of N-(2-hydroxyethyl)ethylenediamine and 56 g of a 40% dimethylamine aqueous solution was added dropwise at 30 to 40°C. The dropping time was 1 hour. Then add 80g of caustic soda.
Add as a 50% aqueous solution and heat and stir at 38-40°C for 1 hour. The dithiocarbamic acid content of the mixed soda 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 96% based on the amine. The subsequent operations were performed in a nitrogen stream. Equimolar amounts of this reaction solution and manganous chloride were reacted in a concentrated aqueous solution. The resulting precipitate was washed three times by decanting to give a slurry containing 30% product. 12 dissolved in 25 g of water to 400 g of this slurry
g of zinc nitrate hexahydrate solution was added and mixed. The resulting mixture was stirred for 1 hour at 25-30°C, then filtered with suction and washed three more times with water. 40-50
It was dried under reduced pressure at 5 to 20 mmHg. Let this product number be 16. Analysis value CS ₂ 49.59% Mn 18.02% Zn 1.86% Production example 6 Mixed soda salt obtained in the same manner as Production example 5 was double decomposed with an equimolar amount of cupric chloride to produce a slurry containing 30% product. And so. 400g of this slurry dissolved in 25g of water 20
g of cupric chloride dihydrate solution was added and mixed.
The mixture was stirred for 1 hour at 25-30°C, then filtered with suction and washed with water three more times. It was subjected to vacuum drying at 40-50°C/5-20 mmHg. Analysis value CS ₂ 45.92% Cu 21.55% Product number 28. Production Example 7 The polydithiocarbamic acid represented by the general formula (A) used was that of Production Example 3, and the following monofunctional dithiocarbamate was used. No. Monofunctional dithiocarbamate (B) (a) Sodium dimethyldithiocarbamate (b) Sodium monomethyldithiocarbamate (c) Sodium aminodithiocarbamate This polydithiocarbamate (A) and monofunctional dithiocarbamate The water-soluble salts of (B) were combined at a molar ratio of 1:2 to form equimolar amounts of a metal salt selected from zinc, iron manganese, and copper. The subsequent treatments were carried out in the same manner as in Production Example 5. The obtained product is as follows.

[Table] Production Example 8 Product 100 mainly composed of composite manganese salt of anhydrous N-(2-hydroxyethyl)ethylenebisdithiocarbamic acid and dimethyldithiocarbamic acid
g and 3 g of zinc oxide were uniformly mixed. product number
29. Production Example 9 45 g of 37% formaldehyde aqueous solution was added to 230 g of 28% sodium ethylene bisdithiocarbamate aqueous solution with stirring at 50°C, and after reacting for 20 minutes, 30% sodium dimethyl dithiocarbamate was added.
109 g of aqueous solution was added and cooled to room temperature. The manganous chloride necessary for metathesis of this reaction mixture solution was reacted in a concentrated aqueous solution. The resulting precipitate was washed by decanting to give a slurry containing 30% product. To 400 g of this slurry was added and mixed a solution of 12 g of zinc nitrate hexahydrate dissolved in 25 g of water. After stirring for 1 hour at 25-30°C, the mixture was filtered and washed with water. It was dried under reduced pressure at 40-50°C/20mmHg. Product number is 29. Analysis value CS ₂ 45.7% Mn 16.5% Zn 2.1% Example 1 Using a small glass sprayer, a diluted solution of the test chemical at a predetermined concentration was applied to the third true leaf of a cucumber (variety Tokiwa No. 3) grown in a iron house. It was sprayed.
(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. Regarding drug damage, (-) means no drug damage, (±) almost no drug damage, (+) means drug damage, and (++) means severe drug damage.

【table】

[Table] Example 2 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 unbalanced 292G manufactured by Rohm and Haas, the weight was 2, titanium oxide was 1, and Solvesso 150 was 0.65.
I used a product that could be blended and mixed completely using a roller mill. This paint was uniformly mixed in a ratio of 95 parts by weight and 5 parts by weight of the agent of the present invention (400 mesh or less), and a 0.005 mm doctor plate was used on a soft iron test piece according to JIS-G-3303. Apply and heat treat. 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.

【table】

[Table] Example 3 Fresh water containing mainly diatoms was put into a beaker 1, the chemical of the present invention was added thereto, and after being gently stirred, it was left for one week. The effect of the chemicals on the algae in the beaker was that they all turned white and died. Flavobacterium also 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 chain or a lower alkylene chain separated by at least one nitrogen atom, and Y or Y ^- represents hydrogen or a hydroxy lower alkyl group (provided that Y and
Except when Y ^- also represents hydrogen. ). ] A water-soluble salt of bisdithiocarbamic acid and a water-soluble salt of lower alkylene bisdithiocarbamic acid, or a water-soluble salt of diethylenetriamine or triethylenetetramine bisdithiocarbamic acid, or the general formula (However, A and B represent hydrogen, a lower alkyl group, or an amino group.) Obtained by metathesis of a water-soluble salt of monodithiocarbamic acid with a water-soluble manganese salt or a water-soluble copper salt. An agricultural and industrial microbicide characterized by containing as an active ingredient a dithiocarbamic acid mixed metal salt in which zinc or copper is combined with a dithiocarbamic acid mixed single metal salt.