JPH021122B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to the provision of a new agricultural and industrial microbicide, and its purpose is to exhibit outstanding effects, to have low toxicity to the human body and useful organisms, and to eliminate the effects on the human body and useful organisms after acting. Concerning agricultural and industrial microbicides that do not leave any harmful effects on the skin. To explain in more detail, the present invention has the general formula [However, X represents an ethylene group, a propylene group, a metaxylylene group, or a -C ₂ H ₄ -NH-C ₂ H ₄ - group. Y is

【formula】

【formula】

【formula】

【formula】

[Formula] or

[Formula] is shown. (However, R is hydrogen, a hydroxyl group, a linear or branched lower alkoxyl group, a phenoxyl group,
para-lower alkylphenoxyl group, R ₁ is hydrogen or methyl group, R ₂ is higher alkyl group, phenoxycarbonyl group, straight-chain or branched lower alkoxycarbonyl group, hydroxy-lower alkoxycarbonyl group, straight-chain or branched Branched lower alkylamino lower alkoxycarbonyl group, cyano group, aminocarbonyl group, sodium sulfonato group, sodium xanthogenyl group, R ₃ is lower alkyl group, R ₄
represents a chloro atom or a methyl group. ) One or more water-soluble salts of dithiocarbamic acids shown in [2] and water-soluble metal salts of metals selected from iron, cobalt, zinc, nickel, manganese, and copper are reacted in the presence of an oxidizing agent and an inorganic acid. The present invention relates to an agricultural and industrial microbicide containing a compound produced by the above method as an active ingredient. Next, to explain the method for producing the active ingredient of the present invention, for example, the above N-substituted polydithiocarbamic acid soluble salt is dissolved in water, and while vigorously stirring, an oxidizing agent, an inorganic acid, and a water-soluble metal salt are added. The solid produced by dropping the mixed solution can be produced separately. The reaction temperature is carried out at -10 to 50°C, preferably in the range of 0 to 10°C. Further, the N-substituted polydithiocarbamic acid soluble salt of the present invention may contain an aliphatic polydithiocarbamic acid soluble salt, such as an ethylene bisdithiocarbamic acid soluble salt or a propylene bisdithiocarbamic acid soluble salt. A preferable product can also be obtained by reacting a water-soluble metal salt with a water-soluble metal salt in the presence of an oxidizing agent and an inorganic acid. The product of the present invention is presumed to be a polydithiocarbamate metal salt, its thiuram sulfide, or a complex salt thereof, and although it is difficult to specify its structure, it exhibits excellent biological activity. . The products of the invention are obtained by varying the amounts of oxidizing agent, inorganic acid and water-soluble metal salt added. Examples of the oxidizing agent include hydrogen peroxide, bleaching powder, sodium hypochloride, chlorine, and in some cases air oxidation. Examples of inorganic acids include sulfuric acid, phosphoric acid, hydrochloric acid, and nitric acid. The metal part used in the water-soluble metal salt is preferably zinc, manganese, iron, copper, nickel, cobalt, calcium or magnesium. Specifically, these metal sulfates,
These include hydrochloride, phosphate, nitrate, acetate, etc. The composite of the present invention is generally 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 with further improved stability.
Stabilizers may be added during production or during formulation. Urea as a stabilizer,
Thiourea, hexamethylenetetramine, paraformaldehyde, 0-tolyl biguanide, diphenylguanidine, NN'-dimethylol urea, N
-Methylurea, NN'-dimethylurea, etc. When the composite of the present invention is used for agricultural and horticultural purposes, it is generally free from phytotoxicity and has a high pest control effect. When using the compound of the present invention, it is possible to apply it directly as it is, but it is also possible to apply it directly as it is, but it is also possible to use a suitable liquid carrier, solid carrier, emulsifying dispersant, etc. according to the agricultural chemical formulation method known in the art. It can be applied in any form such as an aqueous solution, powder, wettable powder, granule, emulsifier, flow dust, tablet, oil, suspension, foaming agent, or atomizer. 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, methylcellulose, starch, gum arabic, polyvinyl alcohol, polyvinyl acetate, and the like. In addition, auxiliary agents 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. In addition, the drug of the present invention has sterilization, insecticidal, acaricidal, herbicidal,
It can also be used in combination with plant growth regulators and the like. 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. 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 50% N-(2,3-dihydroxypropyl)ethylenebisdithiocarbamate sodium 13.3
(0.02 mol) and 10 ml of water are mixed and stirred to form a homogeneous solution. Add to this 1 g (0.01 mol) of concentrated sulfuric acid, 35%
A mixed solution of 1 g (0.01 mol) of hydrogen peroxide and 2.7 g (0.01 mol) of a 50% zinc chloride aqueous solution dissolved in 20 ml of water was heated at 0 to 10°C with vigorous stirring.
dripped over time. 1 at 0-10℃ after dropping
After stirring for an hour, the formed precipitate was filtered and washed with water. This was dried at 60℃/10mmHg under reduced pressure.
A yellow solid was obtained. Let it be composite number 1. The composite obtained from the following raw materials according to this production example is as follows. Sodium N-(2,3-dihydroxypropyl)ethylenebisdithiocarbamate (0.04 mol), H ₂ SO ₄ (0.03 mol), H ₂ O ₂ (0.03 mol) and
ZnCl ₂ (0.01 mol), compound number 2. N-(2,3
-dihydroxypropyl) propylene bisdithiocarbamate sodium (0.04 mol), H ₂ SO ₄
(0.05 mol), H ₂ O ₂ (0.05 mol), ZnCl ₂ (0.01 mol)
Composite number 3. N-(3-isopropoxy-2-
hydroxypropyl) ethylenebisdithiocarbamate (0.06 mol), H ₂ SO ₄ (0.01 mol), H ₂ O ₂ (0.01 mol) ZnCl ₂ (0.05 mol), Compound No. 4. Sodium N-(3-methoxy-2-hydroxypropyl)propylene bisdithiocarbamate (0.02 mol), H ₂ SO ₄ (0.01 mol), H ₂ O ₂
(0.01 mol), ZnCl ₂ (0.01 mol) Composite No. 5. N
-(3-paramethylphenoxy-2-hydroxypropyl)ethylenebisdithiocarbamate sodium (0.02 mol), H ₂ SO ₄ (0.01 mol), H ₂ O ₂
(0.01 mol), ZnCl ₂ (0.01 mol) Composite No. 6. N
-(3-phenoxy-2-hydroxypropyl)ethylenebisdithiocarbamate sodium (0.02 mol), H ₂ SO ₄ (0.01 mol), H ₂ O ₂ (0.01 mol), ZnCl ₂ (0.01 mol) composite Number 7. N-(2
-Phenyl-2-hydroxyethyl)ethylenebisdithiocarbamate (0.02 mol),
H ₂ SO ₄ (0.01 mol), H ₂ O ₂ (0.01 mol), ZnCl ₂ (0.01
Mol) Compound No. 8. N-(3-methoxy-2-
Hydroxypropyl) Sodium ethylenebisdithiocarbamate (0.02 mol), H ₂ SO ₄ (0.01 mol), H ₂ O ₂ (0.01 mol) ZnCl ₂ (0.01 mol) Compound No. 9. N-(2-hydroxypropyl)-m
- Sodium xylylene bisdithiocarbamate (0.06 mol), H ₂ SO ₄ (0.01 mol), H ₂ O ₂ (0.01 mol), ZnCl ₂ (0.05 mol) Compound No. 10. N-(2
-mercaptopropyl) ethylene bisdithiocarbamate (0.06 mol), H ₂ SO ₄ (0.01 mol),
H ₂ O ₂ (0.01 mol), ZnCl ₂ (0.05 mol) Compound no.
11. N-(2-mercaptopropyl)-m-xylylenebisdithiocarbamate sodium (0.06 mol), H ₂ SO ₄ (0.01 mol), H ₂ O ₂ (0.01 mol), ZnCl ₂
(0.05 mol) Compound number 12. Sodium N-octylethylenebisdithiocarbamate (0.05 mol),
H ₂ SO ₄ (0.01 mol), H ₂ O ₂ (0.01 mol), ZnCl ₂ (0.04
Mol) Compound No. 13. Sodium N-(2-aryloxycarbonylpropyl)propylene bisdithiocarbamate (0.02 mol), H ₂ SO ₄ (0.01 mol),
H ₂ O ₂ (0.01 mol), ZnCl ₂ (0.02 mol) Compound no.
14. Sodium N-(2-isopropoxycarbonylpropyl)ethylenebisdithiocarbamate (0.02 mol), H ₂ SO ₄ (0.01 mol), H ₂ O ₂ (0.01 mol), ZnCl ₂ (0.01 mol) Compound No. 15 . N-[2
-(2-Hydroxy)ethoxycarbonylethyl] propylene bisdithiocarbamate sodium (0.02 mol), H ₂ SO ₄ (0.01 mol), H ₂ O ₂ (0.01 mol), ZnCl ₂ (0.01 mol) Compound number 16. N-[2
-(2-N,N dimethylamino)ethoxycarbonylpropyl] propylene bisdithiocarbamate sodium (0.06 mol), H ₂ SO ₄ (0.01 mol), H ₂ O ₂
(0.01 mol), ZnCl ₂ (0.05 mol) Compound No. 17. N
-(2-methoxycarbonylethyl)ethylenebisdithiocarbamate sodium (0.02 mol),
H ₂ SO ₄ (0.01 mol), H ₂ O ₂ (0.01 mol), ZnCl ₂ (0.01
Mol) Compound number 18. Sodium N-(2-ethoxycarbonylethyl)ethylenebisdithiocarbamate (0.02 mol), H ₂ SO ₄ (0.01 mol), H ₂ O ₂ (0.01
mol) ZnCl ₂ (0.01 mol) Compound No. 19. N-(2
-isobutoxycarbonylpropyl) ethylene bisdithiocarbamate (0.02 mol) H ₂ SO ₄
(0.01 mol), H ₂ O ₂ (0.01 mol) ZnCl ₂ (0.01 mol)
Composite number 20. Sodium N-(2-methoxycarbonylpropyl)ethylenebisdithiocarbamate (0.02 mol), H ₂ SO ₄ (0.01 mol), H ₂ O ₂ (0.01 mol), ZnCl ₂ (0.01 mol) Compound No. 21. N-(2
-Ethoxycarbonyl-2-hydroxy-1
-Methyl ethyl) ethylenebisdithiocarbamate (0.02 mol), H ₂ SO ₄ (0.01 mol), H ₂ O ₂
(0.01 mol), ZnCl ₂ (0.01 mol) Compound No. 22. N
-(2-cyanoethyl)ethylenebisdithiocarbamate sodium (0.02 mol), H ₂ SO ₄ (0.01 mol),
H ₂ O ₂ (0.01 mol), ZnCl ₂ (0.01 mol) Compound no.
twenty three. Sodium N-(2-aminocarbonylethyl)ethylenebisdithiocarbamate (0.02 mol),
H ₂ SO ₄ (0.01 mol), H ₂ O ₂ (0.01 mol), ZnCl ₂ (0.01
Mol) Compound No. 24. Sodium N-parachlorobenzylethylene bisdithiocarbamate (0.06 mol), H ₂ SO ₄ (0.01 mol), H ₂ O ₂ (0.01 mol), ZnCl ₂
(0.05 mol) Compound No. 25. Sodium N-paramethylbenzylethylenebisdithiocarbamate (0.05 mol), H ₂ SO ₄ (0.01 mol), H ₂ O ₂ (0.01 mol), ZnCl ₂ (0.04 mol) Compound No. 26. N-(2
- Sodium sulfonatoethyl) propylene bisdithiocarbamate (0.04 mol), H ₂ SO ₄
(0.03 mol), H ₂ O ₂ (0.03 mol), ZnCl ₂ (0.03 mol)
Composite number 27. N-(2-sodium sulfonatoethyl)diethylenetriaminebisdithiocarbamate sodium (0.04 mol), H ₂ SO ₄ (0.03 mol),
H ₂ O ₂ (0.03 mol), ZnCl ₂ (0.03 mol), compound no.
28. Sodium N-(2-sodium sulfonatoethyl)ethylenebisdithiocarbamate (0.04 mol), H ₂ SO ₄ (0.012 mol), H ₂ O ₂ (0.012 mol),
ZnCl ₂ (0.048), compound number 29. Sodium N-(2-sodium xanthogenylethyl)ethylenebisdithiocarbamate (0.04 mol), H ₂ SO ₄ (0.012
mol), H ₂ O ₂ (0.012 mol), ZnCl ₂ (0.048 mol), compound number 30. Sodium N-(2-sodium xanthogenylpropyl)propylene bisdithiocarbamate (0.04 mol), H ₂ SO ₄ (0.03 mol), H ₂ O ₂
(0.03 mol), ZnCl ₂ (0.03 mol) Compound No. 31. N
-(2,3-dihydroxypropyl)ethylenebisdithiocarbamate sodium (0.02 mol),
H ₂ SO ₄ (0.01 mol), H ₂ O ₂ (0.01 mol), CuCl ₂ (0.01
Mol) Compound number 32. Sodium N-(2,3-dihydroxypropyl)ethylenebisdithiocarbamate (0.03 mol), H ₂ SO ₄ (0.015 mol), H ₂ O ₂
(0.015 mol) FeCl ₃ (0.01 mol) Compound number 33. N
-(2,3-dihydroxypropyl)ethylenebisdithiocarbamate (0.06 mol)
H ₂ SO ₄ (0.03 mol), H ₂ O ₂ (0.03 mol), CoCl ₃ (0.02
Mol) Compound number 34. Sodium N-(2,3-dihydroxypropyl)ethylenebisdithiocarbamate (0.02 mol), H ₂ SO ₄ (0.01 mol), H ₂ O ₂
(0.01 mol), NiCl ₂ (0.01 mol) Compound No. 35. Production Example 2 Mix and stir 32 g of 50% sodium N-(2-sodium xanthogenylcotyl)ethylenebisdithiocarbamate (0.04 mol) and 20 ml of water to make a homogeneous solution. To this, add 1 g of concentrated sulfuric acid (0.01 mol). ), 35%
A mixed solution of 1 g (0.01 mol) of hydrogen peroxide and 12.5 g (0.05 mol) of a 50% aqueous manganese chloride solution dissolved in 20 ml of water was stirred vigorously at 0 to 10°C in a nitrogen stream for 1 hour. It dripped. After the dropwise addition, the mixture was stirred at 0 to 10°C for 2 hours, and the resulting precipitate was filtered in a nitrogen stream and washed with water. This was dried under reduced pressure at 60° C./6 mmHg to obtain a yellow-orange solid. Let this compound number be 36. The structures of X and Y in the dithiocarbamic acid represented by the general formula, which is a raw material component used to produce the composites of the present invention in Production Examples 1 and 2, are illustrated below.

【table】

[Table] Test Example 1 A diluted solution of the test chemical at a predetermined concentration was sprayed using a small glass sprayer when the third true leaf of a cucumber (variety Tokiwa Hikari No. 3) grown in a Firelon house was set.
(Adding a spreading agent). Two days after spraying, the plants were inoculated by spraying with a spore suspension of the cucumber scoliosis bacterium and placed in a greenhouse with a humidity of 90% or higher to encourage bacterial infection. On the 10th day after spraying, the disease severity (class 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.

【table】

【table】

[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 Kago Fukuju) grown in a Firelon house was set. (Addition of spreading agent) Two days after spraying, inoculation was carried out by uniformly spraying a tomato late blight spore suspension. The investigation was conducted by counting the number of diseased leaflets on 5 leaves per plant and 7 leaflets per compound leaf on the 10th day after inoculation (classification was given as 0, 1, or 2) to calculate the control value. The formulation used was a 75% hydrating powder.

【table】

[Table] Example 3 Flavobacterium lactis that causes slime
The drug of the present invention was tested on Flavobacterium and Flavobacterium peregrinum. One platinum loopful of each bacterial suspension was inoculated into Waxmann medium (10 ml) containing the drug of the present invention at a predetermined concentration.
The cells were cultured at 30°C for 3 days, and the presence or absence of bacterial growth was examined.

【table】

【table】

Claims (1)

[Claims] 1. General formula [However, X represents an ethylene group, a propylene group, a metaxylylene group, or a -C ₂ H ₄ -NH-C ₂ H ₄ - group. Y represents [Formula] [Formula] [Formula] [Formula] [Formula] or [Formula]. (However, R is hydrogen, a hydroxyl group, a linear or branched lower alkoxyl group, a phenoxyl group,
para-lower alkylphenoxyl group, R ₁ is hydrogen or methyl group, R ₂ is higher alkyl group, phenoxycarbonyl group, straight-chain or branched lower alkoxycarbonyl group, hydroxy-lower alkoxycarbonyl group, straight-chain or branched Branched lower alkylamino lower alkoxycarbonyl group, cyano group, aminocarbonyl group, sodium sulfonato group, sodium xanthogenyl group, R ₃ is lower alkyl group, R ₄
represents a chloro atom or a methyl group. )] and a water-soluble metal salt of a metal selected from iron, cobalt, zinc, nickel, manganese and copper in the presence of an oxidizing agent and an inorganic acid. An agricultural and industrial microbicide characterized by containing as an active ingredient a compound produced by