JPS6412242B2 - - Google Patents

Description

[Detailed description of the invention]

An object of the present invention is to provide an agricultural and industrial microbicide that has the effect of preventing or suppressing the growth and proliferation of harmful organisms and has low toxicity to useful organisms. A large number of alkylene bisdithiocarbamate compounds are known, and most of these are known to be effective as agricultural and industrial drugs. Among these, water-soluble dithiocarbamates have high penetration power and have a large direct effect. It is particularly effective in the early stages of fungal disease outbreaks, however, it has poor residual efficacy. However, it has the characteristic that there is little contamination of the crops to which it is sprayed. In addition, poorly tolerated or insoluble dithiocarbamates include maneb agents, zineb agents, mancozeb agents, and polycarbamate agents, all of which are known as protective fungicides. Compared to water-soluble carbamates, it has a residual effect and is less harmful to the organisms to which it is applied. However, since all of these contain heavy metals, there is a risk of contamination with heavy metals, and therefore, sparingly soluble or insoluble dithiocarbamates that contain little or no heavy metals are desired. Therefore, as a result of intensive research, the present inventor has arrived at the present invention. The present invention is based on the general formula [However, X is a lower alkylene group or at least one
4 separated by nitrogen atoms forming lower alkylene groups of at least 2 carbon atoms each
Denotes a group of hydrocarbons containing 1 or more carbon atoms. Y represents a lower alkyl group having one hydroxyl group. ] A water-soluble metal salt selected from zinc, manganese, iron, and copper is reacted with the product obtained by reacting the ammonium salt of N-substituted alkylene bisdithiocarbamic acid shown in the formula with a lower aliphatic aldehyde in a solution. The present invention relates to a novel agricultural and industrial microbicide containing the resulting product as an active ingredient. The method for producing the drug of the present invention will be explained. An ammonium salt solution of N-substituted alkylene bisdithiocarbamic acid represented by the above general formula is prepared. Next, a solution of a lower aliphatic aldehyde is immediately added to this prepared solution. At this time, the reaction temperature is maintained at 0 to 60° C. and stirred, and a water-soluble metal salt selected from zinc, manganese, iron, and copper is added to this slurry for reaction. The product thus formed is isolated as a solid. When the product is thoroughly washed with water and quantitatively analyzed for metals in the product, it is found that it contains metals as shown in the production example below. Further, the N-substituted alkylene bisdithiocarbamate ammonium salt may be added dropwise to the lower aliphatic aldehyde aqueous solution, or the water-soluble metal salt may be added to the slurry formed by dropping both simultaneously. A desirable drug of the present invention is obtained. Examples of the lower aliphatic aldehyde used in the present invention include formaldehyde, acetaldehyde, halogenated acetaldehyde, cycloacetaldehyde, and chloral. The lower aliphatic aldehyde is used in a 1:1 to 1:3 molar ratio to the N-substituted alkylene bisdithiocarbamate. The water-soluble metal salt is one or more selected from the group consisting of zinc, manganese, iron, and copper, and specifically includes, for example, zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, manganese chloride, and manganese sulfate. , manganese nitrate, manganese acetate, copper chloride, copper sulfate, copper nitrate, copper acetate, iron chloride, iron sulfate, iron nitrate,
Examples include iron acetate. The amount of water-soluble soluble salt is N
-substituted alkylene bisdithiocarbamate in a molar ratio of 1:0.01 to 1:1. Although the product of the present invention is presumed to be an alkylene bisdithiocarbamate compound, its structure cannot be specified. The product is removed from the reaction mixture by filtration, then washed with water or alcoholic medium and dried. It is sparingly soluble or insoluble in water, alcohol, etc. The products of the invention exhibit excellent efficacy as agricultural and industrial microbicides. In addition, it has very little phytotoxic effect on useful organisms. When the products of the invention are used for agricultural purposes, they may be applied directly as such or may be prepared using any solid carrier, liquid carrier and emulsified dispersion according to formulation methods commonly known in the art. It can be applied in any dosage form such as granules, powders, emulsions, wettable powders, flowables, flow dusts, tablets, oils, and aerosols. These carriers include water, alcohol, benzene, xylene, toluene, alkylnaphthalene,
Cyclohexane, paraffin, ether, ester, acetone, methyl ethyl ketone, methyl isobutyl ketone, kerosene, freon, clay talc, kaolin, bentonite, acid clay, diatomaceous earth, calcium carbonate, white carbon, quartz alumina, methyl cellulose, starch, gum arabic, polyvinyl alcohol , polyvinyl acetate, and the like. In addition, adjuvants commonly used in formulations, such as surfactants such as spreading agents, emulsifiers, and dispersants, include soaps, higher alcohol sulfates, alkyl sulfonates, alkylaryl sulfonates, quaternary Grade ammonium salts, polyalkylene oxides, lignin sulfonates, etc. can be blended as appropriate. Further, a stabilizer that is usually used for stabilizing alkylene bisdithiocarbamate metal salts may be added at the same time. Stabilizers include urea, paraformaldehyde, hexamethylenetetramine, O-tolyl biguanide, diphenylguanidine, diaminotoluene, 1,8-3,6-diedomethylene-1,3,6,8-tetraazicyclodecane,
N,N'-dimethylolurea, 1,3,5-tris(cyanomethyl)hexahydrotriazine, N
-methylurea, N,N'-dimethylurea and the like. The compounds of the present invention can also be used simultaneously with other fungicidal, insecticidal, acaricidal, herbicidal, plant growth regulators, etc. Furthermore, when used for industrial purposes, it is possible to prevent contamination and damage caused by mold and other microorganisms that occur in the coating film, and also to prevent contamination by slime, algae, etc. that occur in cooling water, etc. The present invention will be explained in more detail using specific examples, but the present invention is not limited to these specific examples. Production Example 1 58 g of 50% diammonium N-(2-hydroxyethyl)ethylenebisdithiocarbamate
(0.1 mol) was added to 500 ml of water to make a homogeneous solution.
Add to this 16.8g (0.2mol) of 37% formalin aqueous solution.
was added dropwise at room temperature while stirring. After dripping, 45
Stirred at ℃ for 30 minutes. Next, 13.6g of 50% zinc chloride
(0.05 mol) was gradually added dropwise at room temperature while stirring. The white precipitate formed is filtered, washed with water, and
It was dried under reduced pressure at ℃/20 mmHg. Let product number be 1. The metallic zinc content was 9.96% [calculated value 9.92%]. Production Example 2 The product obtained according to the above production example is as follows. The following polydithiocarbamic acid diammonium salts were used.

[Table] Diammonium thiocarbamate

[Table] Um The following aliphatic lower aldehydes were used. Number: Aliphatic lower aldehyde (B) (a) Formalin (b) Acetaldehyde The above polydithiocarbamate diammonium salt
(A) and lower aliphatic aldehyde (B) were reacted at a molar ratio of 1:2, and the reaction was further completed with a water-soluble metal salt selected from copper, manganese, iron, and zinc.

[Table] Test Example 1 When the third true leaf of a cucumber (cultivar Tokiwa Hikari No. 3) grown in a Firelon house was set, a diluted solution of the test chemical at a predetermined concentration was sprayed using a small glass sprayer.
(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 higher to encourage the onset of infection. On the 10th day after spraying, the disease severity (grade 0 to 4) was investigated on the top two leaves that developed at the time of spraying, and the control value was calculated. The formulation used was a 75% hydrating powder. The results are shown in the table below. Regarding drug damage, (-) indicates no drug damage, (±) indicates almost no drug damage, (+) indicates drug damage, and () indicates significant drug damage.

[Table] Test Example 2 A diluted solution of the test chemical at a predetermined concentration was sprayed using a small power sprayer when the 7th true leaf of a tomato (cultivar Kagoshima Fukuju) grown in a Firelon house was removed (spreading agent was added). . 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 following day, the number of infected 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. The formulation used was a 75% hydrating powder.

[Table] Test example 3 Flavobacterium lactis that causes slime
and Flavobacterium peregrinum were tested. A loopful of each bacterial suspension was inoculated into a Waxmann medium (10 ml) containing a predetermined concentration of the precipitated product of the present invention, and cultured at 30° C. for 3 days to determine the presence or absence of bacterial growth.

[Table] Shown.

Claims (1)

[Claims] 1. General formula [However, X represents a lower alkylene group or a hydrocarbon group containing 4 or more carbon atoms separated by at least one nitrogen atom to form a lower alkylene group of at least 2 carbon atoms each. . Y represents a lower alkyl group containing one hydroxyl group. Adding a water-soluble metal salt selected from zinc, manganese, iron and copper to the product obtained by reacting the ammonium salt of N-substituted alkylene bisdithiocarbamic acid shown in ] with a lower aliphatic aldehyde in a solution. An agricultural and industrial microbicide characterized by containing a reaction product as an active ingredient.