JPH1129567A - Heterocyclic compound and fungicide for agricultural and horticultural use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the subject new compound exhibiting remarkable controlling action on various plant blights such as rice blast, apple scab and late blight of tomato and usable as an active component of a new fungicide for agricultural and horticultural use. SOLUTION: This compound is a heterocyclic compound of the formula I (R<1> is H or a 1-6C alkyl; A is O or S; R is phenyl or a 4 to 6-membered heterocyclic group containing 1-3 hetero atoms selected from O, S and N; R is not 2-thienyl when A is O), e.g. the compound of the formula II. The compound of the formula I can be produced by reacting a compound of the formula III with a compound of the formula TBDPS-X (TBDPS is t-butyldiphenylsilyl; X is a halogen) in the presence of a base and an inert solvent reacting the product with a compound of the formula, M-AH (M is an alkali metal atom) and subjecting the reaction product successively to cyclization reaction, deprotection reaction, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel heterocyclic compound and a fungicide for agricultural and horticultural use containing the compound as an active ingredient.

[0002]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies to create a novel fungicide for agricultural and horticultural use.
The heterocyclic compound represented by (I) is a novel compound not described in the literature, and has a remarkable control activity against plant diseases such as rice blast, apple scab, tomato late blight, and cucumber downy mildew. And completed the present invention.

[0003]

According to the present invention, there is provided a compound of the general formula (I ')

Embedded image (Wherein, R ¹ represents a hydrogen atom or a C ₁ -C ₆ alkyl group,
A represents an oxygen atom or a sulfur atom, and R represents a phenyl group or the same or different, and has 4 to 3 hetero atoms selected from an oxygen atom, a sulfur atom or a nitrogen atom.
It represents a 6-membered heterocyclic ring, and the 4- to 6-membered heterocyclic ring may be condensed with a phenyl ring or a 6-membered heterocyclic ring having 1 to 3 nitrogen atoms to form a fused heterocyclic ring. However, when A represents an oxygen atom, R excludes a 2-thienyl group. And the general formula (I) including the general formula (I ′)

[0004]

Embedded image (Wherein, R ¹ represents a hydrogen atom or a C ₁ -C ₆ alkyl group,
A represents an oxygen atom or a sulfur atom, and R represents a phenyl group or the same or different, and has 4 to 3 hetero atoms selected from an oxygen atom, a sulfur atom or a nitrogen atom.
It represents a 6-membered heterocyclic ring, and the 4- to 6-membered heterocyclic ring may be condensed with a phenyl ring or a 6-membered heterocyclic ring having 1 to 3 nitrogen atoms to form a fused heterocyclic ring. The present invention relates to a fungicide for agricultural and horticultural use containing a heterocyclic compound represented by the formula (1) as an active ingredient.
In the definition of R of the heterocyclic compound represented by the general formula (I) of the present invention, “4 may have the same or different and may have 1 to 3 hetero atoms selected from an oxygen atom, a sulfur atom or a nitrogen atom. A 4- to 6-membered heterocyclic ring, which may be condensed with a phenyl ring or a 6-membered heterocyclic ring having 1 to 3 nitrogen atoms to form a fused heterocyclic ring. " For example, a furyl group, a thienyl group, a pyrrolyl group, a benzothienyl group,
And a group such as an indole group, a pyridyl group, an imidazolyl group, and a purinyl group.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION As a typical method for producing a heterocyclic compound represented by the general formula (I ') of the present invention, the following method can be exemplified.

Embedded image (Where R, R ¹ and A are the same as above, and TBDPS
Represents a tertiary butyldiphenylsilyl group, X represents a halogen atom, and M represents an alkali metal atom. )

Structural formula (X) → Structural formula (VIII) The compound represented by the structural formula (X) is reacted with the compound represented by the general formula (IX) in the presence of a base and an inert solvent. The compound represented by the structural formula (VIII) can be produced. The inert solvent used in the present reaction may be any inert solvent that does not significantly inhibit the progress of the present reaction, and examples thereof include halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride, and aromatic solvents such as benzene, toluene, and xylene. Group hydrocarbons, nitriles such as acetonitrile and benzonitrile, linear or cyclic ethers such as dimethyl ether, diglyme, dioxane, tetrahydrofuran (THF), dimethylformamide (DMF), dimethylacetamide (DMA), dimethoxyethane (DM
E), amides such as 1,3-dimethylimidazolidinone, 1-methyl-2-pyrrolidinone, phosphoric amides such as hexamethylphosphoric triamide (HMPA), dimethyl sulfoxide (DMSO), sulfolane, water, etc. And these inert solvents can be used alone or in combination of two or more.

As the base used in this reaction, imidazoles are generally used, but the present invention is not limited to these bases. The amount of base used is the structural formula
The compound represented by formula (X) may be appropriately selected for use from a range of equivalent to 5 equivalents. Since this reaction is an equimolar reaction, the compound represented by the structural formula (X) and the compound represented by the general formula (IX) may be used in equimolar amounts, but any one of the reactants is used in excess. You can also.

[0008] The reaction temperature of this reaction may be appropriately selected from the range of -50 ° C to 200 ° C, and preferably 0 ° C.
C. to 50.degree. The reaction time of this reaction is not fixed depending on the reaction scale, the reaction temperature and the like, but it is sufficient that this reaction is completed, and is in the range of several minutes to 48 hours. After completion of the reaction, the target compound represented by the structural formula (VIII) may be isolated according to a conventional method, and if necessary, a purification operation can be performed by preparative thin-layer chromatography or the like.
As the compound represented by the structural formula (X) and the compound represented by the general formula (IX), those commercially available as reagents and the like can be easily obtained.

Structural Formula (VIII) → General Formula (V) + General Formula (VI) A compound represented by the structural formula (VIII) and a compound represented by the general formula (VII) are prepared in the presence of an inert solvent. By reacting, the compounds represented by the general formulas (V) and (VI) can be produced. As the inert solvent that can be used in this reaction, for example, in addition to the inert solvent that can be used in the production method described above, for example, alcohols such as methanol, ethanol, propanol, and butanol can also be used. As the compound represented by the general formula (VII), for example, hydroxides or hydrosulfides of alkali metals such as sodium hydroxide, sodium hydrosulfide, potassium hydroxide and potassium hydrosulfide can be used. The amount may be appropriately selected from the range of equimolar to excess molar with respect to the compound represented by Structural Formula (VIII), and these may be used as they are or dissolved in water or the like.

[0010] The reaction temperature of this reaction may be appropriately selected from the range of -50 ° C to 100 ° C, and is preferably 0 ° C.
C. to 50.degree. The reaction time of this reaction is not fixed depending on the reaction scale, the reaction temperature and the like, but it is sufficient that this reaction is completed, and is in the range of several minutes to 48 hours. After completion of the reaction, the target compound represented by the general formula (V) or (V)
It can be obtained as a mixture of I) and can be purified by preparative thin-layer chromatography or the like. The general formula (V) and the general formula (VI) can be isolated respectively.

Formula (VI) → Formula (V) The compound represented by Formula (VI) is reduced by a reducing agent in the presence of an inert solvent to give a compound represented by Formula (V). Can be produced. As the inert solvent that can be used in this reaction, for example, an inert solvent that can be used in the production method can be exemplified. As the reducing agent used in the present invention, for example, a reducing agent such as NaBH ₄ can be used, and the amount of the reducing agent to be used is about 1 to 2 moles per mole of the compound represented by the general formula (VI). Can be used. The reaction may be carried out at a temperature ranging from 10 ° C. to the boiling point of the inert solvent used, and preferably at around room temperature. Although the reaction time of this reaction is not constant depending on the reaction scale, the reaction temperature, etc., it is sufficient that this reaction is completed.
The range is about 8 hours. After completion of the reaction, the target compound represented by the general formula (V) may be isolated according to a conventional method, and purification and the like can be carried out if necessary.

General formula (V) → General formula (III) The compound represented by the general formula (V) and the compound represented by the general formula (IV) are ring-bonded in the presence of an inert solvent, a dehydrating agent and a catalyst. The compound represented by the general formula (III) can be produced by the chemical reaction. As the inert solvent that can be used in this reaction, for example, aromatic hydrocarbons such as benzene, toluene, and xylene can be exemplified. As the dehydrating agent in the present cyclization reaction, for example, molecular sieve or the like can be used, and the amount thereof may be used in a large excess with respect to the compound represented by the general formula (V). In order to promote the progress of this reaction, the reaction can be carried out by adding a catalytic amount of, for example, tosyl alcohol or the like as a catalyst. The reaction may be carried out at a temperature ranging from 10 ° C. to the boiling point of the inert solvent used, and preferably at around room temperature. The reaction time of this reaction is not fixed depending on the reaction scale, the reaction temperature and the like, but it is sufficient that this reaction is completed, and is in the range of several minutes to 48 hours. After completion of the reaction, the target compound represented by the general formula (III) may be isolated according to a conventional method, and purification and the like can be carried out if necessary.

Formula (III) → Formula (Ib) The compound represented by the formula (III) is reacted with a compound represented by the formula (III) in the presence of an inert solvent and a deprotecting base to give a compound represented by the formula (Ib). Can be produced. As the inert solvent that can be used in this reaction, for example, dimethyl ether,
Ethers such as diclime, dioxane and tetrahydrofuran can be exemplified. As the deprotecting base used in the present invention, for example, a quaternary ammonium salt such as tetrabutylammonium fluoride can be used. The amount of the quaternary ammonium salt used is 0 to the compound represented by the general formula (III). An amount of about 1 mol to equimolar can be used. The reaction may be carried out at a temperature ranging from 10 ° C. to the boiling point of the inert solvent used, and preferably at around room temperature. The reaction time of this reaction is not fixed depending on the reaction scale, the reaction temperature and the like, but it is sufficient that this reaction is completed, and is in the range of several minutes to 48 hours. After completion of the reaction, the target compound represented by the general formula (Ib) may be isolated according to a conventional method,
Purification and the like can be performed as necessary.

General formula (Ib) → General formula (Ia) The compound represented by the general formula (Ib) and the compound represented by the general formula (II) are generally subjected to the presence of an inert solvent and a base. By reacting below, a compound represented by the general formula (Ia) can be produced. This reaction can be carried out in the same manner as in the production method to produce the desired product.

In the following, typical examples of the compound represented by the general formula (I) are shown in Table 1, but the present invention is not limited to these.

Embedded image

[0016]

[Table 1]

[0017]

[Table 2]

Hereinafter, typical examples of the present invention will be illustrated, but the present invention is not limited thereto. Example 1-1. Production of (2S) -O-tert-butyldiphenylsilylglycidyl

Embedded image (R) -glycidol 1.4 in 15 ml of chloroform
54 g (19.6 mmol) were dissolved and 2.67 g (39.3 mmol) of imidazole and 6.1 ml of tert-butyldiphenylsilyl chloride (23.
5 mmol), and the mixture was stirred at room temperature for 18 hours to carry out a reaction. After completion of the reaction, the desired product was extracted from the reaction solution with chloroform (20 ml × 3), the extracts were combined, dried over sodium sulfate, and the solvent was distilled off under reduced pressure. Purification by layer chromatography (hexane / ethyl acetate = 6: 1) gave 1.882 g of the desired product as a colorless oil. (Yield: 31%)

Mass spectrum (m / z) [FAB; KI
Addition, C ₁₉ H ₂₄ O ₂ SiK (M + K) ⁺ ] found 351.1179 calculated 351.11
83 infrared chromatography [ν _max (neat) / cm ^-1 ] 3070, 3050, 3000, 2960, 2930, 2900, 2860. H-NMR [400 MHz, CDCl ₃ , δ value] 1.06 (9H, s, t-Bu ), 2.61 (1H, dd, J = 2.52 + 5.27,3-H), 2.74
(1H, dd, J = 4.12 + 5.04,3-H), 3.12 (1H, m, 2-H), 3.71 (1H, d
d, J = 4.59 + 11.92,1-H), 3.85 (1H, dd, H = 3.21 + 11.91,1-H),
7.32-7.69 (10H, m, phenyl). C-NMR [100MHz, CDCl, δ value] 19.2 (t-Bu-4 °), 26.7 (t-Bu), 44.4 (3-C), 52.2 (2- C),
64.3 (1-C), 127.7,129.7,135.5,135.6 (phenyl), 133.2
(C-ipso of phenyl).

Embodiment 1-2. (2R) -1-O-tert-butyldiphenylsilyl-3-mercapto-1,
2-propanediol and 3,3-dithiobis (1-O
-Tert-butyldiphenylsilyl-1,2-propanediol)

Embedded image 1.123 g of (2S) -O-tert-butyldiphenylsilylglycidyl in 10 ml of tetrahydrofuran
(3.59 mmol), and 10 ml of a 15-18% aqueous solution of sodium hydrosulfide and ethanol 20 were added to the solution.
The mixture was added to the mixture and stirred at room temperature for 3 hours to carry out a reaction. After completion of the reaction, the desired product was extracted from the reaction solution with chloroform (30 ml × 3). The extracts were combined, dried over sodium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to preparative thin-layer chromatography. (Hexane / ethyl acetate =
By purifying in 4: 1), 0.707 g of the desired product was obtained as a colorless oil. (Yield: 57%) At the same time, 0.422 g of a by-product 3,3-dithiobis (1-O-tert-butyldiphenylsilyl-1,2-propanediol) was obtained as a colorless oil. (Yield: 34%)

(2R) -1-O-tert-butyldiphenylsilyl-3-mercapto-1,2-propanediol mass spectrum (m / z) [FAB; KI added, C ₁₉ H ₂₆
O ₂ SSiK (M + K) ⁺ ] actual value 385.1066 calculated value 385.10
60 infrared chromatography [ν _max (neat) / cm ^-1 ] 3400, 3050, 3030, 2940, 2920, 2880, 2850. H-NMR [400 MHz, CDCl ₃ , δ value] 1.07 (9H, s, t-Bu ), 1.38 (1H, t, J = 8.06, OH), 2.59 (1H, dd,
J = 4.88, SH), 2.67 (2H, m, 3-H), 3.70 (2H, m, 1-H), 3.75 (1
H, m, 2-H), 7.38-7.67 (10H, m, phenyl). C-NMR [100MHz, CDCl, δ value] 19.2 (t-Bu-4 °), 26.8 (t-Bu), 27.7 ( 3-C), 65.6 (1-C),
72.5 (2-C), 127.8, 129.9, 135.5 (phenyl), 132.9 (phenyl
C-ipso).

3,3-dithiobis (1-O-tert-butyldiphenylsilyl-1,2-propanediol) mass spectrum (m / z) [FAB; KI added, C ₃₈ H ₅₀
O ₄ S ₂ Si ₂ K (M + K) ⁺ ] Found 729.2323 Calculated 729.23
26 Infrared chromatography [ν _max (neat) / cm ^-1 ] 3400, 3050, 3030, 3000, 2940, 2920, 2880, 2850. H-NMR [400 MHz, CDCl ₃ , δ value] 1.06 (18H, s, t -Bu), 1.26 (2H, s, OH), 2.62-2.91 (4H, m, 3,
3'-H), 3.55-4.00 (6H, m, 1,1 ', 2,2'H), 7.36-7.65 (20H, m,
Phenyl). C-NMR [100 MHz, CDCl, δ value] 19.2 (t-Bu-4 °), 26.8 (t-Bu), 36.1, 41.9 (3,3'-C), 6
6.2, 66.4 (1,1'-C), 70.7, 71.0 (2,2'-C), 127.5, 129.
8, 135.8 (phenyl), 133.0 (phenyl C-ipso).

Example 1-3-3,3-Dithiobis (1-
Reduction of O-tert-butyldiphenylsilyl-1,2-propanediol)

Embedded image 3,3-dithiobis (1-O-tert-butyldiphenylsilyl-1,2-propanediol) 0.499
g (0.722 mmol) was dissolved in 10 ml of ethanol, and 0.546 g of sodium borohydride was added to the solution.
(14.4 mmol), and the mixture was stirred at room temperature for 4 hours to carry out a reaction. After completion of the reaction, the reaction solution was concentrated, and the desired product was extracted with hexane (20 ml × 3).
It was dried over sodium sulfate, concentrated under reduced pressure, and the obtained residue was purified by preparative thin-layer chromatography (hexane / ethyl acetate = 4: 1) to give the desired product in 0.2%.
04 g was obtained. (Yield: 41%) At the same time, 0.143 g of 3,3-dithiobis (1-O-tert-butyldiphenylsilyl-1,2-propanediol) was recovered. (Recovery rate: 30%)

Embodiment 1-4. (5R) -5- (O-tert-butyldiphenylsilyl-hydroxymethyl)
Production of 2- (2-furyl) -1,3-oxathiolane

Embedded image (2R) -1-O-tert-butyldiphenylsilyl-3-mercapto-1,2-propanediol 0.2
04 g (0.589 mmol) of chloroform 10 ml
To the solution, and add 0.085 g of 2-furaldehyde to the solution.
(0.883 mmol), molecular sieve 3A (Mo
1 g of lecular Sieves 3A) and a catalytic amount of tosyl alcohol were added, and the mixture was stirred at room temperature for 2 hours to carry out a reaction. Then, sodium hydrogen carbonate was added to the reaction solution to stop the reaction. Next, the target substance was extracted from the reaction solution with chloroform (20 ml × 3), and the extracts were combined and dried over sodium sulfate.
The mixture was concentrated, and the obtained residue was purified by preparative thin-layer chromatography (hexane / ethyl acetate = 4: 1) to obtain 0.225 g of the desired product. (Yield: 90%) Next, the obtained target product was separated into α-form and β-form by liquid chromatography.

[0025]

Embedded image Mass spectrum (m / z) [FAB; KI added, C ₂₄ H ₂₉
O ₃ SSi (M + H) ⁺ ] Found 425.1588 Calculated 425.16
07 Infrared chromatography [ν _max (neat) / cm ^-1 ] 3070, 3050, 2960, 2930, 2860.

H-NMR [400 MHz, CDCl ₃ , δ value] (α-type) 1.06 (9H, s, t-Bu), 3.11 (1H, dd, J = 6.95 + 10.37, methyl-H),
3.30 (1H, dd, J = 5.73 + 10.26, methyl-H), 3.81 (2H, m, 4-H), 4.
88 (1H, m, 5-H), 6.15 (1H, s, 2-H), 6.32 (1H, m, furan-4H), 6.
41 (1H, m, furan-3H), 7.35-7.68 (11H, m, phenyl, furan 5-H).

(Β-type) 1.06 (9H, s, t-Bu), 3.15 (1H, dd, J = 8.78 + 10.00, methyl-H),
3.23 (1H, dd, J = 5.49 + 10.12, methyl-H), 3.84 (1H, dd, J = 6.10 +
10.73,4-H), 3.97 (1H, dd, J = 4.76 + 10.61,4-H), 4.23 (1H,
m, 5-H), 6.11 (1H, s, 2-H), 6.32 (1H, m, furan-4H), 6.41 (1H,
m, furan-3H), 7.35-7.68 (11H, m, phenyl, furan 5-H).

Embodiment 1-5. Production of (5R) -5-hydroxymethyl-2- (2-furyl) -1,3-oxathiolane

Embedded image (5R) -5- (O-tert-butyldiphenylsilyl-hydroxymethyl) -2- (2-furyl) -1,
0.191 g (0.433 mmol) of 3-oxathiolane was dissolved in 5 ml of tetrahydrofuran, and 0.22 ml of tetrabutylammonium fluoride was added to the solution.
(0.22 mmol, 1 M solution / tetrahydrofuran) was added, and the mixture was stirred at room temperature for 2 hours to carry out a reaction. After completion of the reaction, the reaction solution was concentrated, and the obtained residue was subjected to preparative thin-layer chromatography (hexane / ethyl acetate = 2: 1).
By purifying the desired product as a colorless oily substance in 0.1.
083 g was obtained. (Yield: 95%) Next, the obtained target product was separated into α-form and β-form by liquid chromatography.

[0029]

Embedded image Mass spectrum (m / z) [FAB, C ₈ H ₁₁ O ₃ S (M + H)
⁺ ] Actual 187.0428 Calculated 187.004
29 Infrared chromatography [ν _max (neat) / cm ^-1 ] 3400, 2930, 2880.

H-NMR [400 MHz, CDCl ₃ , δ value] (α-type) 1.80 (1H, brs, OH), 3.05 (1H, dd, J = 8.29 + 10.25, methyl-H),
3.22 (1H, dd, J = 5.61 + 10.25, methyl-H), 3.74 (1H, dd, J = 5.25 +
11.83,4-H), 3.87 (1H, dd, J = 3.42 + 11.95,4-H), 4.43 (1H,
m, 5-H), 6.22 (1H, s, 2-H), 6.35 (1H, m, furan-4H), 6.47 (1H,
m, furan-3H), 7.44 (furan-5H).

(Β-type) 1.80 (1H, brs, OH), 3.16 (2H, m, methyl-H), 3.80 (1H, dd, J = 5.
49 + 12.08,4-H), 3.93 (1H, dd, J = 3.17 + 11.95,4-H), 4.26
(H, m, 5-H), 6.14 (1H, s, 2-H), 6.35 (1H, m, furan-4H), 6.47
(1H, m, furan-3H), 7.44 (furan 5-H). Light intensity (α-form) [α] ²⁰ _D -133.36 ° (C 1.57, CHCl ₃ ) (β-form) [ α] ²⁰ _D 53.435 ° (C 1.58, CHCl ₃ )

The heterocyclic compound represented by the general formula (I) of the present invention is useful as a fungicide for agricultural and horticultural use, such as rice blast (Pyricularia oryzae) and rice sheath blight (Rhizoctonia soybean).
lani), powdery mildew on various host plants such as Erysiphe graminis such as barley and wheat, and rust on oats (Puccinia coronata) and other plants. Rust,
Tomato blight (Phytophthara infestans) and other plant blight, cucumber downy mildew (Pseudoperonospora cubens)
is), downy mildew of grape (Plasmopara viticola) and other mildew of plants, apple scab (Venturia inaequalis)
), Apple leaf spot (Alternaria mali), pear black spot (Alternaria kikuchiana), citrus black spot (Di
aporthe citr), Pseudomonas species, such as cucumber spot bacterial disease (Pseudomonas syringae pv. lachrymans),
Tomato wilt (Pseudomonas solanacearum), Xanthomonas species, such as cabbage black rot (Xanthomonas campestri
s), rice blight (Xanthomonas oryzae), citrus canker (Xanthomonas citri), bacterial diseases such as Erwinia species such as cabbage soft rot (Erwinia carotovora), and viral diseases such as tobacco mosaic virus. It has an extremely high control effect against diseases.

The fungicide for agricultural and horticultural use containing the heterocyclic compound represented by the general formula (I) of the present invention as an active ingredient damages paddy crops, field crops, fruit trees, vegetables, other crops, flowers and the like. Since it has a remarkable control effect on the disease, according to the time when the occurrence of the disease is predicted, before the occurrence of the disease or at the time when the occurrence is confirmed, paddy fields, fields, fruit trees, vegetables, other The desired effect of the agricultural / horticultural fungicide of the present invention can be obtained by treating paddy water, foliage, or soil of crops, flowers, and the like. The fungicide for agricultural and horticultural use of the present invention,
In general, it is generally used by formulating it into a convenient form in accordance with a conventional method for pesticide formulation. That is, the general formula of the present invention
The heterocyclic compound represented by (I) may be dissolved, separated, suspended, mixed, impregnated, adsorbed or mixed with a suitable inert carrier or, if necessary, in an appropriate ratio together with an auxiliary. It may be adhered and formulated into an appropriate dosage form, for example, a suspension, emulsion, liquid, wettable powder, granule, powder, tablet or the like.

The inert carrier which can be used in the present invention may be either solid or liquid. Examples of the material which can be a solid carrier include soybean flour, cereal flour, wood flour, bark flour, saw flour, Tobacco stem flour, walnut shell flour, bran, fibrous powder, residue after extracting plant extract, synthetic polymers such as pulverized synthetic resin, clays (eg, kaolin, bentonite, acid clay), talcs (eg, talc, pyrophyllide) Etc.), silicas (for example, diatomaceous earth, silica sand, mica, white carbon [synthetic high-dispersion silicic acid also called hydrous finely divided silicon or hydrous silicic acid, some of which contain calcium silicate as a main component depending on the product]), activated carbon, sulfur powder , Pumice, calcined diatomaceous earth, crushed bricks, fly ash, sand, calcium carbonate, inorganic phosphate powders such as calcium phosphate, ammonium sulfate,
Examples include chemical fertilizers such as phosphorous, nitrate, urea, and salt, and composts, and these are used alone or in the form of a mixture of two or more.

The material which can be a liquid carrier is selected from those having a solvent function per se and those capable of dispersing the active ingredient compound with the aid of an adjuvant even without the solvent function. The following carriers can be exemplified as typical examples. These can be used alone or in the form of a mixture of two or more types. Examples thereof include water, alcohols (eg, methanol, ethanol, isopropanol, butanol, ethylene glycol, etc.), ketones (For example, acetone, methyl ethyl ketone, methyl isobutyl ketone,
Diisobutyl ketone, cyclohexanone, etc.), ethers (eg, ethyl ether, dioxane, cellosolve,
Dipropyl ether, tetrahydrofuran, etc.), aliphatic hydrocarbons (eg, kerosene, mineral oil, etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, solvent naphtha, alkylnaphthalene, etc.), halogenated hydrocarbons (eg, dichloroethane) , Chloroform, carbon tetrachloride, chlorinated benzene, etc.), esters (eg, ethyl acetate, diisopropyl phthalate, dibutyl phthalate, dioctyl phthalate, etc.), amides (eg, dimethylformamide, diethylformamide, dimethylacetamide, etc.), nitriles (For example, acetonitrile and the like), dimethyl sulfoxides and the like.

As the other adjuvants, there may be mentioned the following adjuvants. These adjuvants are used according to the purpose, and may be used alone or in combination of two or more adjuvants. In some cases, however, it is possible to use no auxiliaries. Surfactants are used for the purpose of emulsifying, dispersing, solubilizing and / or wetting the active ingredient compound, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene higher fatty acid ester, polyoxyethylene Resin acid ester, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkyl aryl sulfonate, naphthalene sulfonic acid condensate,
Surfactants such as lignin sulfonate and higher alcohol sulfate can be exemplified. For the purpose of stabilizing the dispersion of the active ingredient compound, adhering and / or binding, the following exemplified auxiliaries can be used. For example, casein, gelatin, starch, methylcellulose, carboxymethylcellulose, acacia, polyvinyl Auxiliaries such as alcohol, pine oil, bran oil, bentonite, ligninsulfonate and the like can also be used.

The following auxiliaries can be used for improving the flowability of the solid product. For example, auxiliaries such as wax, stearate, alkyl phosphate and the like can be used. As peptizers for suspension products, auxiliary agents such as, for example, naphthalenesulfonic acid condensates, condensed phosphates and the like can also be used. As an antifoaming agent, for example, an auxiliary agent such as silicone oil can be used. The compounding ratio of the active ingredient compound can be adjusted according to need. For example, 0.01 to 50% by weight in the case of powder or granules, and 0.01 to 50% in the case of emulsion or wettable powder. % By weight is appropriate.

The fungicide for agricultural and horticultural use of the present invention is used for controlling various diseases as it is, or is appropriately diluted or suspended in water or the like, and the amount effective for controlling the disease is predicted. It can be used by applying it to crops or places where generation is not preferable.For example, for the purpose of controlling disease of paddy rice, application of water surface to rice, application of rice nursery box, application of seed dressing for direct sowing of flooded seeds, seeds It can be used by a disinfection method or the like, and can be used by spraying on stems, leaves and the like against diseases such as wheat and treating it with soil or the like and absorbing it from the roots.

The amount of the fungicide for agricultural and horticultural use of the present invention depends on various factors, for example, the purpose, the target disease, the growing condition of the crop, the tendency of the disease to occur, the weather, the environmental conditions, the dosage form, the application method, the application place, and the application. Although it fluctuates depending on the timing and the like, the active ingredient compound may be appropriately selected from the range of 0.01 g to 10 kg per 10 ares according to the purpose. The fungicide for agricultural and horticultural use of the present invention can be further used in combination with another fungicide for agricultural and horticultural use for the purpose of extending the disease to be controlled and the suitable period of control, or for reducing the amount of medicine.

The following are typical formulation examples and test examples of the present invention, but the present invention is not limited to these.
In addition, in the formulation examples, "parts" indicates parts by weight. Formulation Example 1 Compound shown in Table 1 50 parts Xylene 40 parts Mixture of polyoxyethylene nonylphenyl ether and calcium alkylbenzenesulfonate 10 parts The above are uniformly mixed and dissolved to form an emulsion. Formulation Example 2 Compounds described in Table 1 3 parts Clay powder 82 parts Diatomaceous earth powder 15 parts The above are uniformly mixed and pulverized to obtain a powder.

Formulation Example 3 Compounds listed in Table 1 5 parts Mixed powder of bentonite and clay 90 parts Calcium ligninsulfonate 5 parts The above components were mixed uniformly, kneaded by adding an appropriate amount of water, and granulated.
Dry to granules. Formulation Example 4 Compounds described in Table 1 20 parts Kaolin and synthetic highly dispersed silicic acid 75 parts Mixture of polyoxyethylene nonylphenyl ether and calcium alkylbenzenesulfonate 5 parts .

Test Example 1 Rice blast control test by water surface application Rice grown in pots of 1/14000 ares (5-6
At the leaf stage), a drug containing the compound shown in Table 1 as an active ingredient was applied to the surface of the water at a rate of 200 g / 10a as an active ingredient, left in a greenhouse for 1 week, and then treated with rice blast (Pyriculari).
a oryzae) by spray inoculation. After inoculation, leave in a wet room for 1 day, transfer to a greenhouse, and leave it for 6 days to cause sufficient disease, then investigate the number of lesions on each leaf, and calculate the control value in comparison with the untreated plot. The determination was made according to the following criteria. A: Control value 100-95% B: Control value 94-85% C: Control value 84-60% D: Control value 59-0% The results are shown in Table 2.

Test Example 2 Apple Scab Control Test Potted apple containing the compound of the present invention as an active ingredient 2
A chemical solution of 00 ppm was sufficiently sprayed, and one day after the treatment, a spore suspension of apple scab (Venturia inaequalis) was spray-inoculated. After inoculation, place the cells in a humid room at 17 ° C for one day, and then leave them in a constant temperature room at 17 ° C for 10 days to cause sufficient disease.
The lesion area was investigated, compared with the untreated plot, and the control effect was determined in the same manner as in Test Example 1. The results are shown in Table 2.

Test Example 3 Cucumber downy mildew control test A 200 ppm solution containing the present compound as an active ingredient was sprayed on a potted cucumber (two-leaf stage), and one day later, a zoospore suspension of downy mildew (Pseudoperonospora cubensis) was spray-inoculated. After inoculation, the plants were left for 1 day in a humid room at 25 ° C., and further left in a greenhouse for 6 days to cause sufficient disease. The judgment was made. The results are shown in Table 2.

[0045]

[Table 3]

Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI C07D 411/04 C07D 411/04 (72) Inventor Yoshinobu Yamamoto 1-4-1-625, Mikadai, Kawachinagano-shi, Osaka (72) Inventor Masaaki Kudo 4-12-8 Okayama, Shijonawate City, Osaka Prefecture

Claims (6)

[Claims] 1. A compound of the general formula (I ′) (Wherein, R ¹ represents a hydrogen atom or a C ₁ -C ₆ alkyl group,
A represents an oxygen atom or a sulfur atom, and R represents a phenyl group or the same or different, and has 4 to 3 hetero atoms selected from an oxygen atom, a sulfur atom or a nitrogen atom.
It represents a 6-membered heterocyclic ring, and the 4- to 6-membered heterocyclic ring may be condensed with a phenyl ring or a 6-membered heterocyclic ring having 1 to 3 nitrogen atoms to form a fused heterocyclic ring. However, when A represents an oxygen atom, R excludes a 2-thienyl group. And a heterocyclic compound represented by the formula: 2. The heterocyclic compound according to claim ¹ , wherein R ¹ is a hydrogen atom. 3. The heterocyclic compound according to claim 1, wherein the 4- to 6-membered heterocyclic ring or fused heterocyclic ring is a thienyl group, a furyl group or an indole group. 4. A compound of the general formula (I) (Wherein, R ¹ represents a hydrogen atom or a C ₁ -C ₆ alkyl group,
A represents an oxygen atom or a sulfur atom, and R represents a phenyl group or the same or different, and has 4 to 3 hetero atoms selected from an oxygen atom, a sulfur atom or a nitrogen atom.
It represents a 6-membered heterocyclic ring, and the 4- to 6-membered heterocyclic ring may be condensed with a phenyl ring or a 6-membered heterocyclic ring having 1 to 3 nitrogen atoms to form a fused heterocyclic ring. A fungicide for agricultural and horticultural use, comprising the heterocyclic compound represented by the formula (1) as an active ingredient. 5. The agricultural and horticultural fungicide according to claim 4, wherein R ¹ is a hydrogen atom. 6. The fungicide for agricultural and horticultural use according to claim 5, wherein the 4- to 6-membered heterocyclic ring or fused heterocyclic ring is a thienyl group, a furyl group or an indole group.