JP3343449B2 - Fungicide composition for soil or seed treatment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The object of the present invention is to have a broad antibacterial spectrum, a long residual effect,
To provide a combined fungicide for treating soil or seeds having a synergistic effect.

[0002]

The present invention relates to a novel agricultural and horticultural compounded fungicide having excellent bactericidal activity.

[0003]

2. Description of the Related Art 2-
(4-Fluorophenyl) -1- (1H-1,2,4-
Triazol-1-yl) -3-trimethylsilyl-2
-Propanol (hereinafter referred to as compound (I)) has activity as an agricultural and horticultural fungicide, and is disclosed in Japanese Patent Application No. 4-267234.
Issue.

The compound (I) has a therapeutic and preventive effect on many plant diseases, and when used as a spray or a water application agent, it can control the important diseases of rice cultivation such as sheath blight and blast. Can be strongly controlled. In addition, by using as a soil treatment or seed treatment agent, Rhizocto
In addition to controlling the damping-off disease of various crops such as beet, cotton, wheat, cucumber, and legumes caused by nia fungus, soil such as white silk disease such as eggplant and cucurbit, black bruise of potato, and eye spot disease of wheat Infectious diseases can be effectively controlled.

[0005] In addition, 3 used as an active ingredient of the present invention
-Hydroxy-5-methylisoxazole (hereinafter referred to as compound (II)) is disclosed in JP-B-42-2440,
It is a known compound described in JP-B-48-38148 and the like as a soil fungicide and a growth regulator, and Pyth.
It is effective against a wide range of soil-borne and seed-borne diseases including ium and Aphanomyces, and controls rice seedling wilt, curly seedling, cucumber vine, tomato wilt or beet seedling wilt. Or it is used for the purpose of raising healthy seedlings.

A calcium salt of compound (II) (hereinafter referred to as compound (IIa)) is disclosed in JP-B-48-38148.
In the publication, compound (I) is used against various crop diseases.
It is known to have the same activity as I). In addition, compound (IIa) has a lower volatility than compound (II), and thus is also advantageous as a seed treating agent in this regard.

Further, 1,2-benzisothiazolin-3-one (hereinafter referred to as compound (IIIa)) used as an active ingredient of the present invention is a commercially available industrial fungicide and fungicide, and is a cupric hydroxide. (Hereinafter referred to as compound (IIIb))
Is a commercially available agricultural and horticultural fungicide.

[0008]

However, the compound (I) has no effect on diseases caused by algae such as Pythium and Aphanomyces, and there is a possibility that when applied in an excessively large amount, chemical damage such as growth inhibition may occur.

[0009] Compound (II) and its salts also have problems such as long-lasting potency and slightly weak activity against Rhizoctonia bacteria.

[0010] In view of such circumstances, the present inventors have conducted repeated studies for the purpose of providing an agricultural or horticultural fungicide for treating soil or seeds, which has a wide efficacy spectrum and a long residual effect, and as a result, a compound ( I), compound (II) or a salt thereof, and compound (IIIa) and / or compound (IIIb)
It has been found that a bactericide composition containing the compound exhibits a remarkable synergistic effect as compared to the case where each of them is used alone or in combination of two types, further expands the efficacy spectrum, and significantly enhances the residual effect. Completed the invention.

[0011]

Configuration of the Invention

[0012]

The present invention relates to 2- (4-fluorophenyl) -1- (1H-1,2,4-triazol-1-yl) -3-trimethylsilyl-2-propanol and 3- (4-fluorophenyl) -1- (1H-1,2,4-triazol-1-yl) -3-trimethylsilyl-2-propanol. A fungicidal composition containing hydroxy-5-methylisoxazole or a salt thereof, and 1,2-benzisothiazolin-3-one and / or cupric hydroxide.

As the salt of compound (II), Japanese Patent Publication No. Sho 48
No. 38148, for example, sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, preferably calcium salt, and most preferably,

[0014]

Embedded image

Calcium salt dihydrate of compound (II) (hereinafter referred to as compound (IIa1)). The metal atom and the like in these salts are substituted with the hydrogen atom of the hydroxyl group at the 3-position of the isoxazole ring of compound (II). Compound (IIa1) is obtained by adding 1 equivalent of calcium hydroxide and 2 equivalents of compound (II) to water,
The filtrate is cooled to about 0 ° C., and the precipitated crystals are collected by filtration and dried at 50 to 60 ° C.

The preferred compounding ratio of the active ingredient of the present invention is 1 to 100 parts by weight of compound (II) or a salt thereof, compound (IIIa) and / or (IIIb) per 1 part by weight of compound (I). ) Can be blended at a ratio of 1 to 10 parts by weight, and preferably, compound (II) is 2 to 10 parts by weight, and compound (IIIa) and / or (IIIb) is 1 to 10 parts by weight.
The ratio is 10 parts by weight. The total active ingredient content relative to the total amount of the composition is usually 1 to 50% by weight for liquids, usually 0.3 to 25% by weight for powders, usually 1 to 90% by weight for wettable powders,
In the case of granules, it is usually 0.3 to 25% by weight.

The admixture of the present invention is usually used together with adjuvants conventionally used in the field of formulation. Formulas (I) and (I
The active ingredients of I) can be prepared in a known manner, for example in the form of emulsion stocks, sprayable pastes, sprayable or dilutable solutions, diluted emulsions,
Formulated in wettable powders, aqueous solvents, powders, granules, and capsules, for example, with polymeric substances. In addition, for the purpose of labor saving and safety, etc., suitable water repellents, foaming agents, and the like in the form of agricultural chemicals (granules, tablets, wettable powders, capsules, etc.) which are easily dispersed or dissolved in water or on the water surface, It is also possible to coexist with a spreading agent or the like, wrap it directly in water-soluble paper and throw it into water.

Hereinafter, the present invention will be described in more detail with reference to Examples, Reference Examples and Test Examples, but the present invention is not limited thereto.

[0019]

【Example】

[0020]

Example 1 10 parts of compound (I) and 10 parts of compound (IIa)
1), 5 parts of compound (IIIa), 2 parts of Gohsenol GL-05S (trade name, polyvinyl alcohol, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), Neoperex No. 1 6
After mixing 10 parts of F powder (trade name, sodium dodecylbenzenesulfonate, manufactured by Kao Corporation) and 23 parts of carplex (trade name, hydrous amorphous silicon dioxide, manufactured by Shionogi Pharmaceutical Co., Ltd.), Ec Sample Mill K
The powder was pulverized with a II-I type (hammer mill type pulverizer, manufactured by Fuji Paudal Co., Ltd.) to obtain a powder coating.

[0021]

Example 2 10 parts of compound (I) and compound (IIa)
1), 50 parts of compound (IIIb), 2 parts of Gohsenol GL-05S, Neoperex No. 1 After mixing 10 parts of 6F powder and 23 parts of carplex,
It was pulverized with an Ec Sample Mill KII-I to obtain a powder coating.

[0022]

[Comparative example]

[0023]

Comparative Example 1 Compound (I), 10 parts, Gohsenol GL
-5S, 2 parts, Neoperex No. 10 parts of 6F powder, 23 parts of carplex and NG
A powder coating was obtained in the same manner as in Example 1 using 55 parts (trade name, fine powder of a mineral substance containing kaolinite and sericite as main components, manufactured by Sigleite Co., Ltd.).

[0024]

Comparative Example 2 Compound (IIa1) 50 parts, Gohsenol GL-05S 2 parts, Neoperex No. 1 A powder coating was obtained in the same manner as in Example 1, except that 10 parts of 6F powder, 23 parts of carplex and 15 parts of Ziglite NG were used.

[0025]

Comparative Example 3 Compound (IIIa) (5 parts), Gohsenol GL-05S (2 parts), Neoperex No. A powder coating was obtained in the same manner as in Example 1 using 10 parts of 6F powder, 23 parts of carplex, and 60 parts of iglite NG.

[0026]

Comparative Example 4 1 part of the compound (IIIb), 2 parts of Gohsenol GL-05S, Neoperex No. A powder coating was obtained in the same manner as in Example 1 using 10 parts of 6F powder, 23 parts of carplex and 64 parts of iglite NG.

[0027]

Comparative Example 5 10 parts of compound (I) and compound (IIa)
1) 50 parts, 2 parts of Gohsenol GL-05S, 10 parts of Neoperex NO.6F powder, 23 parts of carplex and 5 parts of Ziglite NG were used in the same manner as in Example 1 to obtain a powder coating. .

[0028]

Comparative Example 6 10 parts of compound (I) and compound (III)
a) 5 parts, Gohsenol GL-05S 2 parts, Neoperex o. A powder coating was obtained in the same manner as in Example 1 using 10 parts of 6F powder, 23 parts of carplex and 50 parts of Ziglite NG.

[0029]

Comparative Example 7 10 parts of compound (I) and compound (III)
b) 1 part, 2 parts of Gohsenol GL-05S, 10 parts of Neoperex NO.6F powder, 23 parts of carplex and 54 parts of Ziglite NG were used to obtain a powder coating in the same manner as in Example 1. .

[0030]

Comparative Example 8 Compound (IIa1) (50 parts) and Compound (I)
IIa), 2 parts of Gohsenol GL-05S, Neoperex No. A powder coating was obtained in the same manner as in Example 1 using 10 parts of 6F powder, 23 parts of carplex and 10 parts of Ziglite NG.

[0031]

Comparative Example 9 Compound (IIa1) (50 parts) and Compound (I)
IIb), 2 parts of Gohsenol GL-05S, 2 parts of Neoperex No. A powder coating was obtained in the same manner as in Example 1 using 10 parts of 6F powder, 23 parts of carplex, and 14 parts of iglite NG.

[0032]

[Test example]

[0033]

[Test Example 1] Sugar beet seedling wilt Sugar beet seedling wilt fungus Aphanomyces cochlioides was grown on a cholesterol-added cornmeal agar medium using Rhizoc.
tonia solani was pre-cultured in an oat medium, the cultured cells were crushed with a blender, and separately mixed and inoculated into field soil.

The wettable powders of Examples 1 and 2, and Comparative Examples 1 to
9 wettable powders were applied to seeds of sugar beet (variety: Monomidori) moistened with water. The sugar beet seeds were sown in the pathogen-contaminated field. Six weeks later, the percentage of healthy seedlings was investigated. Table 1 shows the average of three 10m ² groups in one area.

[0035]

[Table 1] ──────────────────────────────────── Reagents (% ad. / Seed weight ) Healthy seedling rate (%) ─────────────────── ───────── Akfanomyces resectonia (I) (IIa1) (IIIa) ( IIIb) Seedling blight Seedling blight ──────────────────────────────────── Example 1 0.1 0.05 0.005 −100.0 100.0 0.005 0.025 0.0025 −100.0 100.0 Example 2 0.01 0.05 − 0.001 100.0 100.0 0.005 0.025 − 0.0005 100.0 100.0 Comparative Example 1 0.01 − − − 0.0 15.0 0.005 − − − 0.0 3.3 Comparative Example 2 − 0.05 − − 35.0 12.0 − 0.025 − − 8.0 0.0 Comparative Example 3 − − 0.005 − 0.0 0.0 − − 0.0025 − 0.0 0.0 Comparative Example 4 − − − 0.001 2.1 0.0 − − − 0.0005 0.0 0.0 Comparative Example 5 0.01 0.05 − − 75.0 82.0 0.005 0.025 − − 40.5 51.0 Comparative Example 6 0.01-0.005-0.0 18.0 0.00 5 − 0.0025 − 0.0 15.5 Comparative Example 7 0.01 − − 0.001 0.0 25.0 0.005 − − 0.0005 0.0 10.8 Comparative Example 8 − 0.05 0.005 − 58.0 25.3 − 0.025 0.0025 − 35.5 15.0 Comparative Example 9 − 0.05 − 0.001 48.0 16.0 − 0.025 − 0.0005 23.3 13.8 No treatment 0.0 0.0 薬 No phytotoxicity was observed in any of the plots Was.

[0036]

[Reference example]

[0037]

Reference Example 1 1-chloro-2- (4-fluorophenyl) -3-trimethylsilyl-2-propanol 2-chloro-4'-fluoroacetophenone (8.63
g, 0.05 mol) in ether (60 ml) and trimethylsilylmethylmagnesium chloride (200 ml, 0.057 mol of ether solution) in a nitrogen stream with stirring, while the temperature of the reaction mixture exceeds 15 ° C. to 20 ° C. The mixture was added dropwise at a constant rate, and then stirred at room temperature for 1 hour. The reaction solution was poured into 200 ml of ice water, adjusted to pH 6 to 7 with 5% hydrochloric acid, and extracted with 100 ml of ethyl acetate. The organic layer was washed with saturated saline (50 ml × 2), and the organic layer was dried (Na ₂ S).
O ₄ ) and evaporation to give a crude oil, which was purified by silica gel column chromatography (ethyl acetate: n-hexane =
1: 10 → 1: 5) to give 8.8 g (yield 67.7%) of an oil as the title compound.

Elemental analysis value: C ₁₂ H ₁₈ ClFOSi; Calculated value (%) C 55.26 H 6.96 Cl 13.59 F
7.26 Analytical value (%) C 55.02 H 6.96 Cl 13.58 F
7.43 NMR spectrum: δ ppm (CDCl ₃ ) −0.18 (9H, s), 1.23 (1H, d, J = 14.7 Hz), 1.45 (1H, d, J = 14.7H)
z), 3.70 (1H, d, J = 11.0Hz), 3.80 (1H, d, J = 11.0Hz), 6.99-
7.09 (2H, m), 7.35-7.43 (2H, m)

[0039]

Reference Example 2 2- (4-fluorophenyl) -1- (1H-1,2,2
4-Triazol-1-yl) -3-trimethylsilyl-2-propanol 60% sodium hydride (1.62 g, 0.04 mol) was added to dimethylformamide (60 ml), and the mixture was cooled and stirred with ice water. The lower 1,2,4-triazole (2.91 g, 0.04 mol) was added. The reaction mixture was further stirred at room temperature for 30 minutes, and then the 1-chloro-2- (4-fluorophenyl) -3- obtained in Reference Example 1 was obtained.
Trimethylsilyl-2-propanol (5.5 g, 0.
021 mol), and the mixture was heated and stirred at 90 ° C. for 30 minutes. Then, the mixture was cooled, poured into ice water (200 ml), extracted with ethyl acetate (300 ml), the ethyl acetate layer was washed with saturated saline (100 ml × 3), and the ethyl acetate layer was dried (Na ₂ SO ₄ ). Evaporation gave a crude oil which was further subjected to silica gel column chromatography (ethyl acetate: hexane = 1: 5 → 1: 1 → 2: 1).
The title compound was obtained. 2.9 g (47% yield) Melting point 118-119 ° C NMR spectrum (CDCl ₃ ) δ ppm: -0.18 (9H, s), 1.16 (1H, d, J = 14.5 Hz), 1.33 (1H, d, J = 14.5H
z), 4.36 (1H, d, J = 14.0Hz), 4.43 (1H, d, J = 14.0Hz), 6.93 ~
7.01 (2H, m), 7.26 to 7.31 (2H, m), 7.91 (1H, s), 7.99 (1H, s) Mass spectrum (M / Z): 293 (M ⁺ ), 278, 211

[0040]

Reference Example 3 Compound (IIa1) 5.7 kg of water, 0.57 kg of calcium hydroxide, and 1.4 kg of 3-hydroxy-5-methylisoxazole were added to a 10-liter glass kolben, and heated and dissolved at 80 ° C. Filtered while hot. The filtrate was cooled to 0 ° C., and the precipitated crystals were collected by filtration and dried at 55 ° C. for 2 hours.
g was obtained. The crude crystals were recrystallized from water to obtain 55
Drying at 2 ° C. for 2 hours gave white crystals.

Melting point: 280 ° C. decomp. Elemental analysis value (as C ₈ H ₈ N ₂ O ₄ Ca.4H ₂ O) Calculated value (%) C: 31.17 H: 5.23 N: 9.09 Actual value (%) C: 31.09 H: 5.24 N: 9.07 IR spectrum ν _max ^KBr cm ^-1 : 3377 (s), 3220 (w), 165
0 (w), 1626 (s), 1510 (s), 1410 (s), 1255 (s), 1150 (s), 1025
(s), 900 (s).

NMR spectrum (D ₂ O) ppm: 2.11 (3H, d, J = 0.
8Hz), 5.36 (1H, q, J = 0.8Hz).

Analytical value of water by Karl Fischer method Water content (as C ₈ H ₈ N ₂ O ₄ Ca · 4H ₂ O) Calculated value (%) 23.37 Observed value (%) 23.62 The compound is 3-hydroxy-5
-Calcium salt dihydrate of methyl isoxazole (compound (IIa1)).

[0044]

Industrial Applicability The fungicide of the present invention effectively controls soil-borne, seed-borne and air-borne plant diseases by contact action and systemic action over a long period of time.

The fungicide of the present invention is effective against plant diseases caused by, for example, the following fungi.

Ascomycetes; Erysiphe, Sclerotinia, Mon
ilinia, Helminthosporium, Pyrenophora, Pseudocerco
sporella, Gaeumannomycetes Basidiomycetes; Ustilago, Puccinia, Tilletia, Rhizoctoni
a Algae; Pythium, Aphanomyces, Achlya Imperfect fungus; Fusarium, Septoria, Phoma, Alternaria It is possible to exceed the effect of using the active ingredient alone and to reduce the amount of the active ingredient to be applied. As a treatment method, soil treatment and seed treatment are possible. In addition, it can be expected to control air-borne diseases such as powdery mildew and rust, and also has an advantage in terms of labor-saving control since the efficacy spectrum is expanded and the work of disinfecting seeds or soil is reduced.

────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-6-279216 (JP, A) JP-A-5-222060 (JP, A) JP-A-7-2607 (JP, A) JP-A-5-222 238911 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A01N 55/00 A01N 53/80 101 A01N 43/80 102 A01N 59/20 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] (1) 2- (4-fluorophenyl) -1- (1
H-1,2,4-triazol-1-yl) -3-trimethylsilyl-2-propanol and 3-hydroxy-
5-methylisoxazole or a salt thereof, and 1,
A fungicide composition containing 2-benzisothiazolin-3-one and / or cupric hydroxide.