JP3307026B2 - Agricultural and horticultural sterilizing composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to an agricultural and horticultural fungicidal composition.

BACKGROUND OF THE INVENTION Conventionally, (Z) -2'-methylacetophenone 4,6-dimethylpyrimidin-2-ylhydrazone, O-ethyl
S, S-diphenyl phosphorodithioate, 4,5
6,7-Tetrachlorophthalide, kasugamycin and the like are used as a controlling agent for plant diseases such as rice blast, that is, a fungicide for agricultural and horticultural use. However, these compounds are not always used depending on the condition of disease occurrence. It is hard to say that a sufficient control effect has been achieved.

[0002]

Means for Solving the Problems In view of such circumstances, the present inventors have conducted intensive studies to develop an excellent agricultural and horticultural fungicide. As a result, (a) the following general formula 2 (B) (Z) -2′-methylacetophenone 4,6-dimethylpyrimidin-2-ylhydrazone, O-ethyl S, S-diphenyl phosphorodithioate, 4,5,6,7 -By using in combination with at least one compound selected from the group consisting of tetrachlorophthalide and kasugamycin,
The present inventors have found that they exert an excellent control effect on plant diseases such as rice blast by synergistic action, and have led to the present invention. That is, the present invention relates to (a) general formula

Embedded image (Wherein X represents a hydrogen atom or a chlorine atom, Y represents a chlorine atom or a bromine atom, and R represents a methyl group or a vinyl group), and (b) (Z) -2 '-Methylacetophenone 4,6-
Dimethylpyrimidin-2-ylhydrazone, O-ethyl S, S-diphenyl phosphorodithioate, 4,
Provided is a fungicidal composition for agricultural and horticultural use (hereinafter, referred to as the composition of the present invention) containing, as an active ingredient, at least one compound selected from the group consisting of 5,6,7-tetrachlorophthalide and kasugamycin. .

[0003] Examples of the amide compound represented by the general formula 2 used in the present invention are shown in Table 1.

[Table 1]

The amide compound represented by the general formula (2) is
It is described in JP-A-2-76846, JP-A-2-76845, or JP-A-1-156951. (Z) -2′-Methylacetophenone 4,6-dimethylpyrimidine-2
-Ilhydrazone (hereinafter referred to as Compound A)
It is described in JP-A-61-21551. O-ethyl S, S
-Diphenyl phosphorodithioate (hereinafter referred to as Compound B
) Are described in JP-B-44-12919.
4,5,6,7-tetrachlorophthalide (hereinafter, referred to as compound C) is described in JP-B-44-32592. Kasugamycin (hereinafter referred to as Compound D) is
Pestiside manual 9th edition, 5
15 pages (published by The British Crop Protection Council)
It is described in.

[0005] Examples of plant diseases to which the composition of the present invention has control effect include, for example, rice blast (Pyricularia oryza).
e), ear blight, sesame leaf blight (Cochliobolus miyabean)
us), streak leaf blight (Sphaerulina oryzina), micrococcal sclerotia (Magnaporthe salvinii), discolored rice and the like. The mixing ratio of (a) an amide compound represented by the general formula (2), which is an active ingredient of the composition of the present invention, and (b) compounds A, B, C and / or D is based on (a) 1 part by weight of the amide compound. for,
(B) The compounds A, B, C and / or D are each usually used in an amount of 0.01 to 1000 parts by weight, preferably 0.02 to 10 parts by weight, from the viewpoint of controlling effect, but further in terms of cost and the like. In consideration of the above, compounds A, B, and C are 0.5 to
5 parts by weight, and the compound D is more preferably 0.1 to 0.5 part by weight. When the composition of the present invention is used as an agricultural and horticultural fungicide, the active ingredient compound is usually mixed with a solid carrier, a liquid carrier or a gaseous carrier, and if necessary, a surfactant and other formulation aids are added. Oils, emulsions, wettable powders, granules, powders, solutions, suspensions, foams, microcapsules,
Formulated into ULV, paste, etc. and used. In these preparations, the total amount of the active ingredient compound is expressed in terms of weight ratio,
The content is 0.1 to 99.9%, preferably 0.2 to 80%. These preparations use, for example, an active ingredient compound as a developing agent, that is, a solid carrier, a liquid carrier, and in some cases, a surfactant, a fixing agent, a dispersing agent, a stabilizer, a foam forming agent, and the like, or a mixture thereof. And mixing. Examples of the solid carrier include clays (for example, kaolin, diatomaceous earth, synthetic hydrated silicon oxide, fubasami clay, bentonite, acid clay), talcs, and other inorganic minerals (for example, sericite, quartz powder, sulfur powder, activated carbon, Fine powders or granules such as calcium carbonate and hydrated silica) can be used. Examples of the liquid carrier include water, alcohols (eg, methanol and ethanol), ketones (eg, acetone and methyl ethyl ketone), and aromatic carbons. Hydrogens (eg, benzene, toluene, xylene, ethylbenzene,
Methylnaphthalene), aliphatic hydrocarbons (for example, n
-Hexane, cyclohexanone, kerosene, kerosene), esters (e.g., ethyl acetate, butyl acetate), nitriles (e.g., acetonitrile, isobutylnitrile), ethers (e.g., dioxane, diisopropyl ether), acid amides (e.g., Dimethylformamide, dimethylacetamide), halogenated hydrocarbons (eg, dichloroethane, trichloroethylene, carbon tetrachloride) and the like. Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenates thereof, polyoxyethylene glycol ethers, polyhydric alcohol esters, and sugar alcohol derivatives. And the like. Examples of the fixing agent and dispersant include casein, gelatin, polysaccharides (eg, starch, gum arabic, cellulose derivatives, alginic acid), lignin derivatives, bentonite, saccharides, synthetic water-soluble polymers (eg, polyvinyl alcohol, polyvinyl pyrrolidone) , Polyacrylic acids) and the like. Examples of the stabilizer include PA
P (isopropyl acid phosphate), BHT (2,6-di-
tert-butyl-4-methylphenol), BHA
(2-tert-butyl-4-methoxyphenol and 3
-Tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, surfactants, fatty acids or esters thereof, and the like. The above-mentioned preparation can be used as it is or diluted with water or the like.More specifically, the above-mentioned preparation is sprayed or powdered on a plant, or sprayed on a water surface or a soil surface of a paddy field or the like, or powdered or powdered,
Alternatively, if necessary, it can be used in various forms such as further mixing with soil. In addition, the composition of the present invention may be used with or without other fungicides, insecticides, acaricides, nematicides, herbicides, plant growth regulators, fertilizers or soil conditioners. Can also. The application rate of the composition of the present invention varies depending on the mixing ratio of the active ingredient compound, weather conditions, preparation form, application time, application method, place of application, target disease, target crop, etc., but the total amount of the active ingredient compound is 1%.
Usually 0.1 to 1000 g per are, preferably 1 g to
100 g, when the emulsion, wettable powder, suspension, liquid preparation, etc. are diluted with water and applied, the application concentration is usually 0.0001 to 0.1% as the total amount of the active ingredient compound,
Granules, powders and the like are applied as they are without any dilution.

[0006]

The present invention will be described in more detail with reference to formulation examples, test examples, etc., but the present invention is not limited to these examples. The parts and percentages used in the formulation examples are parts by weight and% by weight unless otherwise specified. The amide compounds represented by the general formulas 2 are shown by the compound numbers in Table 1. Formulation Example 1 One part of each of the compounds (1) to (5), one part of each of the compounds A to D, 88 parts of kaolin clay and 10 parts of talc are thoroughly pulverized and mixed to obtain 2% powder of each. Formulation Example 2 1.5 parts of each of the compounds (1) to (5), 2.5 parts of each of the compounds A to D, 87 parts of kaolin clay and 9 parts of talc are thoroughly pulverized and mixed to obtain a 4% powder for each. . Formulation Example 3 1 part of each of compounds (1) to (5), each of compounds A to D
2.5 parts, 87 parts of kaolin clay and 9.5 parts of talc are thoroughly pulverized and mixed to obtain 3.5% powder of each. Formulation Example 4 1.5 parts of each of compounds (1) to (5), 2 parts of each of compound A, B or D, 2 parts of compound C, kaolin clay 86
Parts and 8.5 parts of talc are ground and mixed to obtain 5.5% powder of each. Formulation Example 5 2 parts of each of compounds (1) to (5), 2.5 parts of each of compounds A, B or D, 2.5 parts of compound C, kaolin clay 85
Parts and 8 parts of talc are ground and mixed to obtain a 7% powder of each. Formulation Example 6 10 parts of each of the compounds (1) to (5), 20 parts of each of the compounds A to D, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and 64 parts of water were mixed and wet-pulverized. A 30% suspension of each is obtained. Formulation Example 7 10 parts of each of compounds (1) to (5), 20 parts of each of compounds A, B or D, 20 parts of compound C, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic silicon hydroxide Pulverize and mix well, 50
% Wettable powder is obtained. Formulation Example 8 10 parts of each of compounds (1) to (5), 20 parts of each of compounds A to D, 14 parts of polyoxyethylene styryl phenyl ether, calcium dodecylbenzene sulfonate 6
Parts and 50 parts of xylene are mixed well to obtain 30% emulsion of each. Each of the compounds (3) and (4) can be prepared, for example, by the following method. Reference Formulation Example 1 One part of the compound (3) or (4), 90 parts of kaolin clay and 9 parts of talc are thoroughly pulverized and mixed to obtain 1% powder of each. Reference Formulation Example 2 10 parts of either the compound (3) or (4), 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and 84 parts of water were mixed, wet-pulverized, and 10% of each was obtained.
Obtain a suspension. Reference Formulation Example 3 20 parts of either compound (3) or (4), calcium ligninsulfonate 3 parts, sodium lauryl sulfate 2
Parts and 75 parts of synthetic silicon hydroxide are thoroughly pulverized and mixed to obtain a 20% wettable powder for each. Reference Formulation Example 4 15 parts of either compound (3) or (4), 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 6 parts of xylene
Mix well 5 parts to obtain each 15% emulsion. Reference Formulation Example 5 4 parts of either compound (3) or (4), 1 part of synthetic hydrous silicon oxide, 2 parts of calcium ligninsulfonate, 30 parts of bentonite and 63 parts of kaolin clay are thoroughly pulverized and mixed, and water is added. After well kneading, the mixture is granulated and dried to obtain each 4% granule. Other compounds (1),
Each of (2), (5) and A to D can also be prepared, for example, according to these reference preparation examples.

Next, the composition of the present invention is represented by the following general formula (a):
Test examples show that the amide compound represented by the formula (1) or (b) Compound A, B, C, or D has a synergistically superior germicidal effect for agricultural and horticultural use as compared with the case of using each alone. Test Example 1 Preventive effect and residual effect test for rice blast A plastic pot was filled with sandy loam, and rice (Kinki 33
No. 2) and cultivated in a greenhouse for 20 days. The reagent prepared as a wettable powder according to Formulation Example 7 was diluted with water to a predetermined concentration, and the resulting solution was sprayed with foliage so as to sufficiently adhere to the leaf surface of the rice seedling. In the preventive effect test, the spore suspension of the blast fungus was spray-inoculated, respectively, immediately after the chemical solution was air-dried, and in the residual effect test, after being kept in a greenhouse for 7 days. After the inoculation, the plants were kept at 24 ° C. under high humidity for 10 days, and the control effect was examined by the following index. The results are shown in Tables 2 and 3.

[Table 2]

[Table 3]

Test Example 2 Test of therapeutic effect on rice blast A plastic pot was filled with sandy loam, and rice (Kinki 33
No. 2) and cultivated in a greenhouse for 20 days. The rice seedlings were spray-inoculated with a spore suspension of the blast fungus. After inoculation, the cells were kept under a humid condition at 24 ° C. for 1 day to infect the cells.
The reagent prepared in the form of an emulsion was diluted with water to a predetermined concentration according to the above method, and the resulting solution was sprayed on the foliage of the rice seedlings so as to sufficiently adhere to the leaves. After the chemical solution was air-dried, it was kept at 24 ° C. under high humidity for 10 days, and the control effect was examined by a control index according to Test Example 1.
Table 4 shows the results.

[Table 4]

Reference Preparation Example 1 (Production of Compound (3)) 23 g (97.7 mm) of commercially available 4-bromo-2-chlorobenzoic acid
ol), 50 ml of thionyl chloride and 1-2 drops of N, N'-dimethylformamide were added, and the mixture was refluxed for 4 hours. Thionyl chloride was distilled off under reduced pressure to obtain 4-bromo-2-chlorobenzoyl chloride. To this was added 100 ml of anhydrous THF, the mixture was cooled to -78 ° C, and 100 ml (0.1 mol) of a 1M THF solution of methylmagnesium bromide was added dropwise. The reaction temperature was returned to room temperature, and the mixture was stirred for 3 hours. 10% hydrochloric acid 10
After adding 0 ml and stirring for 10 minutes, ethyl acetate was added,
It was washed sequentially with a sodium hydroxide solution and a saline solution. The ethyl acetate layer was dried over anhydrous magnesium sulfate and concentrated, and the obtained crude product was subjected to silica gel chromatography (hexane: ethyl acetate = 10: 1) to give 4′-bromo-2′-chloroacetophenone 19.2. g was obtained. 4'-bromo-2'-chloroacetophenone thus obtained
1.44 g of formic acid and 14.30 g of formamide were added to 19.2 g, and the mixture was stirred at 180 to 190 ° C for 6 hours. The reaction solution was cooled, chloroform was added, and the mixture was washed with brine. The chloroform layer was dried over anhydrous magnesium sulfate and then concentrated to obtain a residue. 10 ml of concentrated hydrochloric acid was added thereto, and 10
Stirred at 0 ° C. for 1 hour. The reaction solution was cooled, and the precipitated crystals were separated by filtration and washed with chloroform (the chloroform layer was discarded). Crystals were dissolved in the aqueous layer of the filtrate, and sodium hydroxide solution was added to the aqueous layer to make it alkaline, followed by extraction with chloroform. The chloroform layer was dried over anhydrous magnesium sulfate, concentrated and concentrated to give 1- (4-bromo-2).
8.34 g of -chlorophenyl) ethylamine were obtained. 1.0 g of 2-cyano-3,3-dimethylbutanoic acid was dissolved in anhydrous tetrahydrofuran, and 1.38 g of carbonyldiimidazole was added at 0 ° C. under a nitrogen atmosphere. The reaction temperature was returned to room temperature and stirred for 1 hour. There, 1- obtained as described above
(4-bromo-2-chlorophenyl) ethylamine 1.83
g of tetrahydrofuran solution was added dropwise at room temperature, and the mixture was stirred at the same temperature for 3 hours. Ethyl acetate was added to the reaction solution, and 1N
The extract was washed successively with an aqueous sodium hydroxide solution, 1N hydrochloric acid and saturated saline. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and the crude product was washed with hexane to give N- [1
-(4-Bromo-2-chlorophenyl) ethyl] -2-
1.40 g of cyano-3,3-dimethylbutanoic acid amide (compound (3)) was obtained. mp 161.0 ° C.'H-NMR (CDCl ₃ / TMS) δ (ppm): 1.
14 and 1.18 (each s, 9H in total), 1.51 and 1.52
(D, J = 6.99 Hz, 9H in total), 3.14 and 3.
16 (each s, total 1H), 5.28-5.39 (m, 1
H), 6.37-6.49 (br, 1H), 7.20 (dd, J = 8.
31 Hz, J = 1.67 Hz, 1H), 7.40 (dd, J = 8.31)
Hz, J = 1.97 Hz, 1H), 7.54 to 7.55 (m, 1H)

Reference Preparation Example 2 (Production of Compound (4)) 2-cyano-3,3-dimethyl-4-pentenoic acid 1.0 g
Was dissolved in anhydrous tetrahydrofuran, and the solution was dissolved at 0 ° C. in a nitrogen atmosphere.
Then, 1.27 g of carbonyldiimidazole was added. The reaction temperature was returned to room temperature and stirred for 1 hour. There reference production example 1
A solution of 1.68 g of 1- (4-bromo-2-chlorophenyl) ethylamine obtained in the first part of the above was added dropwise at room temperature, and the mixture was stirred at the same temperature for 3 hours. Ethyl acetate was added to the reaction solution, and the mixture was washed sequentially with a 1N aqueous sodium hydroxide solution, 1N hydrochloric acid and saturated saline. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and the obtained crude product was washed with hexane to give N- [1- (4-bromo-2-).
Chlorophenyl) ethyl] -2-cyano-3,3-dimethyl-4-pentenoic acid amide (compound (4)) (1.05 g) was obtained. mp 158.0 ° C.'H-NMR (CDCl ₃ / TMS) δ (ppm): 1.
23-1.29 (m, 6H), 1.48 and 1.50 (d, J =
6.88 Hz, 3H in total, 3.23 and 3.25 (each s, 1H in total), 5.10 to 5.23 (m, 2H), 5.30 (q, J = 6.
00Hz, 1H), 5.88-6.00 (m, 1H), 6.22-6.35
(Br, 1H), 7.18 (d, J = 8.30 Hz, 1H), 7.
39 (dd, J = 8.30 Hz, J = 0.65 Hz, 1H), 7.53
7.57.54 (m, 1H)

[0011]

Industrial Applicability The composition of the present invention has an excellent control effect on plant diseases, especially rice blast.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Tsutohiro Kato 4-2-1 Takashi Takarazuka-shi, Hyogo Sumitomo Chemical Co., Ltd. (56) Reference JP-A-3-284603 (JP, A) JP JP-A-61-24508 (JP, A) JP-A-57-21306 (JP, A) JP-A-55-6601 (JP, A) JP-A-54-135225 (JP, A) JP-A-54-23126 (JP , A) JP-A-59-7103 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A01N 37/34 A01N 43/54 A01N 57/14 A01N 43/12 A01N 43/16 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] (A) a compound represented by the following general formula: (Wherein X represents a hydrogen atom or a chlorine atom, Y represents a chlorine atom or a bromine atom, and R represents a methyl group or a vinyl group), and (b) (Z) -2 '-Methylacetophenone 4,6-
Dimethylpyrimidin-2-ylhydrazone, O-ethyl S, S-diphenyl phosphorodithioate, 4,
A fungicidal composition for agricultural and horticultural use, comprising as an active ingredient at least one compound selected from the group consisting of 5,6,7-tetrachlorophthalide and kasugamycin.