JP2002193714A - New fungicidal composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fungicidal composition which exhibits excellent control effects against wide crop diseases, especially plant diseases caused by phycomycetes, and is used for agriculture and horticulture. SOLUTION: This fungicidal composition for agriculture and horticulture contains an oxime derivative of general formula (1) [HetA is a group of formula (2) (R1 is H or the like) or the like; HetB is a group of formula (3) or the like; HetC is phenyl or the like] as the first ingredient and a compound (an anilide-based compound) exhibiting a RNA synthesis-inhibiting property against plant disease pathogenic fungi as the second ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a fungicidal composition having at least two kinds of active ingredients and having a synergistically enhanced effect on disease infection, particularly for controlling plant diseases caused by algae. The present invention relates to a fungicidal composition exhibiting an excellent effect. More specifically, the present invention relates to a composition in which one of the active ingredients is an oxime derivative exhibiting a plant disease controlling action, and the other is an active ingredient compound of an RNA synthesis-inhibiting fungicide, ie, an RNA synthesis-inhibiting fungicide.

[0002]

2. Description of the Related Art Various plants are constantly exposed to infection by phytopathogenic viruses, bacteria and filamentous fungi (hereinafter simply referred to as phytopathogenic fungi) that inhabit the soil, on plants and on weeds. Once these diseases occur once because they are transmitted through soil, water, plants, etc., it is difficult to control them with drugs. Moreover, these diseases cause destruction of the plants, and thus cause destructive damage. For this reason, a number of compounds have been developed as fungicides used for controlling these diseases.

[0003] For example, oxime derivatives are known.
Oxime derivatives are known to be effective against various plant diseases caused by phytopathogenic bacteria (WO99296).
No. 89).

[0004] Examples of the bactericidal compound for inhibiting RNA synthesis include anilide compounds, and further include metalaxyl, benalaxyl, furalaxyl, offrace, oxadixyl, ciprofram and metalaxyl M.

[0005] These include plague, downy mildew, Pythium.
It is prophylactically and therapeutically effective against diseases caused by relatively narrow pathogenic bacteria belonging to algae such as fungi. It is also excellent in showing a permeability effect. However, in recent years, generation of resistant bacteria has become a problem, particularly with drugs such as metalaxyl. In addition, bacteria that have acquired resistance to metalaxyl are also known to exhibit cross-resistance, which is also resistant to other anilide-based compounds such as oxadixyl. In the case of other compounds and drugs having the same mechanism of action, the risk of the cross-resistance is known. Is concerned. Since the emergence of resistant bacteria results in an increase in the amount of the drug and a large burden on the environment, as a countermeasure, it is used as a mixture with a preventive agent or the number of times the drug itself is used is limited. However, it is also desired to reduce the amount of drug used.

Further, many plant diseases (especially plant diseases caused by algae) are once developed, and the symptom progresses rapidly, and the pathogen spreads rapidly by secondary infection. It was difficult to sufficiently control plant diseases caused by algae. However, a fungicide exhibiting a sufficient control action against a wide range of crop diseases under such aggressive conditions, particularly plant diseases caused by algae, has not been known so far.

[0007]

An object of the present invention is to provide a novel fungicide composition for agricultural and horticultural use which exhibits an excellent control effect on plant diseases. More specifically, a novel agricultural and horticultural fungicide composition exhibiting an excellent effect of controlling a wide range of crop diseases under aggressive conditions, particularly plant diseases caused by algae, and such an agricultural and horticultural fungicide composition. An object of the present invention is to provide a method for controlling plant diseases using the same.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, a novel agricultural / horticultural fungicide composition comprising a specific component has been developed over a wide range under aggressive conditions and the like. The present invention was found to exhibit an excellent effect in controlling plant diseases, particularly plant diseases caused by algae, and completed the present invention. That is, the present invention provides, as a first component, the following general formula (1)

[0009]

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[However, HetA is represented by the following two formulas.

[0011]

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Wherein R ¹ is a hydrogen atom, a lower alkyl group, an amino group, or an alkoxy group, and R ² is a hydrogen atom.
B is the following three formulas

[0013]

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Wherein Y represents a lower alkyl group, and HetC is a group represented by the following formula:

[0015]

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Wherein X is a halogen atom and n is 0
~ 3. Oxime derivative (I) represented by
It is intended to provide a fungicide composition for agricultural and horticultural use, which contains a fungicidal compound for inhibiting RNA synthesis (II) as a component.

The present invention also provides a method for controlling plant diseases, particularly plant diseases derived from algae, using the novel fungicide composition for agricultural and horticultural use.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The oxime derivative (I) (hereinafter sometimes simply referred to as “compound (I)”), which is the first component of the agricultural and horticultural fungicide composition of the present invention, has the following general formula (1):

[0019]

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[However, HetA is represented by the following two formulas.

[0021]

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Wherein Q is a hydrogen atom, R ¹ is a hydrogen atom, a lower alkyl group, an amino group or an alkoxy group, and R ² is a hydrogen atom. HetB is the following three formulas

[0023]

Embedded image

Wherein Y represents a lower alkyl group, and HetC is a group represented by the following formula:

[0025]

Embedded image

Wherein X is a halogen atom and n is 0
~ 3. )].

Examples of R ¹ of HetA include a hydrogen atom, a lower alkyl group, an amino group and an alkoxy group.

The lower alkyl group represented by R ^{1 of} HetA includes a methyl group, an ethyl group, a propyl group (n-propyl group, isopropyl group) and a butyl group (tert-butyl group, n-
Butyl group, isobutyl group, sec-butyl group), pentyl group (n-pentyl group, neopentyl group, etc.), 1,1-
Examples thereof include a linear or branched lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as a dimethylpropyl group and a 1-ethylpropyl group, and more preferably a propyl group and a butyl group.

Further, as the R ¹ is an alkoxy group of HetA, methoxy group, an ethoxy group, a propoxy group (n- propoxy group, isopropoxy group), butoxy (tert
-Butoxy group, n-butoxy group, isobutoxy group, se
c-butoxy group), pentoxy group (n-pentyloxy group, neopentoxy group, etc.), 1,1-dimethylpropoxy group, 1-ethylpropoxy group, etc.
6, preferably 1-4 straight-chain or branched lower alkoxy groups, more preferably a propoxy group.

X of HetC is a halogen atom, specifically, a chlorine atom, a bromine atom and a fluorine atom, preferably a chlorine atom or a fluorine atom.

N represents an integer of 0 to 3. When n is 2 or 3, X may be the same or different.

The stereostructure of the oxime moiety present in the oxime derivative represented by the general formula (1) includes an (E) configuration and a (Z) configuration, and these stereoisomers are all included in the present invention. . Usually, the synthetic product is composed of the (E) form and the (Z) form.
They are obtained as a mixture of bodies, which can be isolated from each other by separation and purification.

In the oxime derivative (I), the (Z) -form is particularly superior in plant disease controlling activity to the (E) -form.
In a natural environment, the (Z) body also changes to the (E) body by light or the like, and exists as a mixture at a certain ratio of the (E) body and the (Z) body. The stabilized ratio between the (E) -form and the (Z) -form differs for each compound.

The oxime derivative represented by the general formula (1) of the present invention can be produced by a conventionally known method. For example, it can be produced by the method described in W09929689, and the like.

Table 1 shows specific examples of the compound (I) of the present invention.

[0036]

[Table 1]

[0037]

[Table 2]

Next, the fungicidal compound (II) for inhibiting RNA synthesis, which is the second component of the present invention (hereinafter simply referred to as “compound (I)
I) ". ) Will be described. The RNA synthesis-inhibiting bactericidal compound (II) of the present invention is intended to mean a compound exhibiting an effect of preventing plant diseases and curing by inhibiting RNA synthesis of plant pathogenic bacteria. More specifically, it refers to a compound that has a plant systemic translocation property and has an effect of inhibiting the biosynthesis of ribosomal ribonucleic acid (γRNA) of a plant disease bacterium that has entered a plant, thereby inhibiting the growth and dying of the fungus. RNA synthesis inhibitory fungicidal compound (I
I) is not particularly limited as long as it has such an effect, but preferably includes an anilide-based compound.

Further, specific examples of the anilide compound include metalaxyl (generic name) {chemical name: methyl N- (methoxyacetyl) -N- (2,6-xylyl) -DL-alaninate, page 792}, benalaxyl (Generic name) {chemical name; methyl N- (phenylacetyl) -N- (2,6-xylyl) -DL-alaninate, p. 87}, furaxyl (generic name) {chemical name: methyl N- (2-furoyl) ) -N-
(2,6-xylyl) -DL-alaninate, 634
Page｝, off-race (generic name) ｛chemical name; (±) -α- (2
-Chloro-N-2,6-xylylacetamido) -γ-butyrolactone, page 893３,

Oxazixyl (generic name) {chemical name; 2-
Methoxy-N- (2-oxo-1,3-oxazolidine-3-
Yl) Compound having a 2,6-dimethylanilide structure, such as aceto-2 ', 6'-xylidide, page 907, etc., ciprofram (generic name) {chemical name; (±) -α- [N- (3-chlorophenyl) ) Cyclopropanecarboxamide] -γ-butyrolactone, page 305, etc. and a compound having a 3-chloroanilide structure and metalaxyl M (general name)} Chemical name: Methyl N- (methoxyacetyl) -N- (2,6-xylyl ) -D-alaninate, page 794}, and the like,
Of these, metalaxyl is preferred.

In the above, each page described after the compound name is described in The Pesticide Manual, Eleventh Edition (edit
ed by Clive Tomlin, published by The British Crop P
rotection Council 1997).

Although a scientific theory has not yet been obtained and various theories have been considered, surprisingly, the agricultural and horticultural fungicide composition of the present invention is characterized in that the RNA synthesis-inhibiting fungicidal compound ( By combining the oxime derivative (I) with II), it exhibits an excellent synergistic bactericidal effect and exhibits excellent effects against various plant diseases.

For example, rice blast (Pyricularia oryz)
ae), sesame leaf blight (Cochliobolus miyabeanus), sheath blight (Rhizoctonia solani), barley powdery mildew (Erysip)
he graminis, f. sp.hordei, f. sp. tritici), Fusarium head blight (Gibberella zeae), Rust (Puccinia striiformi)
s, P.graminis, P.recondita, P.hordei), snow rot (Typ
hula sp.Micronectriella nivalis), naked smut (Ustil
ago tritici, U.nuda, stag beetle (Tilletia ca
ries), eye spot disease (Pseudocercosporella herpotrichoide)
s), strain rot (Rhizoctonia cerealis),

[0044] Cloudy disease (Rhynchosporium secalis), leaf blight (Septoria tritici), blight (Leptosphaeria nodo)
rum), citrus black spot (Diaporthe citri), scab (Elsinoe fawcetti), fruit rot (Penicillium digi)
tatum, p.itanicum), Monilia disease of apple (Sclerotin)
ia mali), rot (Valsa mali), powdery mildew (Pod)
osphaera leucotricha), spot leaf spot (Alternaria mal)
i), scab (Venturia inaequalis), pear scab (Venturia nasshicola), black spot (Alternaria kikuch)
iana), scab (Gymnosporangium haraeanum),

Peach ash disease (Sclerotinia cinerea),
Scab (Cladosporium carpophilum), Phomopsis rot (Phomopsis sp.), Grape downy mildew (Plasmopara)
viticola), black rot (Elsinoe ampelina), late rot (Glomerella cingulata), powdery mildew (Uncinula nec)
ator), rust (Phakopora ampelopsidis), oyster anthracnose (Gloeosporium kaki), leaf rot (Cercospora kak)
i, Mycospharerella nawae), downy mildew of cucumber (Pse
udoperonospora cubensis, anthracnose of cucumber (Colleto
trichum lagenarium, powdery mildew (Sphaerotheca ful)
iginea),

Vine blight (Mycosphaerella melonis), tomato ring blight (Alternaria solani), leaf mold (Clado)
sporium fulvum), plague (Phytophthora infestans)
, Eggplant brown spot (Phomopsis vexans), powdery mildew (E
rysiphe cichoracearum, black spot of cruciferous vegetables (A
lternaria japonica), vitiligo (Cercosporella brassi)
cae), green onion rust (Puccinia allii), soybean purpura (Cercospora kikuchii), black rot (Elsinoe gly)
cines), Black spot disease (Diaporthe phaseolorum var.saja)
e), bean anthracnose (Colletotrichum lindemthianu)
m),

Peanut black spot (Mycosphaerella per
sonatum), brown spot (Cercospora arachidicola), pea powdery mildew (Erysiphe pisi), downy mildew (Peronos
pora pisi), downy mildew of broad bean (Peronospora vicia)
e), plague (Phytophthora nicotianae), potato summer plague (Alternaria solani), plague (Phytophthora in
festans), strawberry powdery mildew (Sphaerotheca humul)
i), plague (Phytophthora nicotianae), tea net blight (Exobasidium recticulatum), white scab (Erysiphe l
eucospila), tobacco scab (Alternaria longipe)
s), powdery mildew (Erysiphe cichoracearum),

Anthracnose (Colletotrichum tabacum), plague (Phytophthora parasitica), sugar beet brown spot (Cer
cospora beticola, rose scab (Diplocarpon rosa)
e), powdery mildew (Sphaerotheca pannosa), plague (Phy
tophthora megasperma, chrysanthemum brown spot (Septoria chr)
ysanthemiindici), white rust (Puccinia horiana)
And other various crops such as Botrytis cinerea, Sclerotinia sclerotiorum, Pythium fungi (Pyth
ium sp.), and exhibits an excellent synergistic bactericidal effect in controlling algal fungi such as downy mildew, plague, and diseases caused by pycium.

The mixing ratio of compound (I) and compound (II), which are the active ingredients of the agricultural and horticultural fungicide composition of the present invention, is not particularly limited, but is preferably 1 part by weight of compound (I). Compound (II) is used in an amount of usually 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight.

The fungicide composition for agricultural and horticultural use of the present invention can be used by simply mixing the compound (I) and the compound (II), and usually, the compound (I) and the compound (II) are used.
And a solid carrier, a liquid carrier or / and a gaseous carrier, and if necessary, a surfactant, a fixing agent,
Add dispersing agents, stabilizers, diluents, emulsifiers, spreading agents, formulation aids such as thickeners, wettable powders, suspending agents, granules,

[0051] Powders, dry flowables, emulsions, aqueous solutions, oils, smokers, aerosols, microcapsules, etc. may be used in the form of a formulation, or each of compound (I) and compound (II) may be conventionally known. Formulation into the above dosage form by the method described above, and after further dilution with water as the case may be, the respective preparations are mixed and used. In these preparations, the total amount of compound (I) and compound (II) as active ingredients is usually 0.1 to 99% by weight, preferably 0.2 to 90% by weight.
Contained.

However, solid carriers include, for example, clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, attapulgite clay, bentonite, acid clay, etc.), talcs, and other inorganic minerals (sericite, quartz powder, sulfur powder) , Activated carbon, calcium carbonate, hydrated silica, montmorillonite, mica, vermiculite, gypsum, etc.), salts for chemical fertilizers (ammonium sulfate, phosphorous ammonium, nitrite, urea, salt ammonium, etc.), white carbon, wood flour, starch, alumina, sugar Examples of the liquid carrier include water, alcohols (methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, ethylene glycol, benzyl alcohol, etc.). ), Petroleum fractions (petroleum ether, kerosene, solvent naphtha) ), Aliphatic or alicyclic hydrocarbons (n- hexane, cyclohexane, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone,

Methyl isobutyl ketone, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, chlorobenzene, cumene, methylnaphthalene, etc.),
Halogenated hydrocarbons (chloroform, dichloromethane, dichloroethane, trichloroethylene, carbon tetrachloride, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol acetate, amyl acetate, etc.), nitriles (acetonitrile, propionitrile, acrylonitrile, Isobutyronitrile, etc.), ethers (dioxane, isopropyl ether, ethylene oxide, tetrahydrofuran, etc.),

Acid amides (dimethylformamide, dimethylacetanilide, etc.), sulfoxides (dimethylsulfoxide, etc.), alcohol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.) and the like, and the gaseous carrier as butane gas , Carbon dioxide gas, fluorocarbon gas and the like. Examples of the surfactant include nonionic surfactants (polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester, etc.),

Anionic surfactants (alkyl benzene sulfonate, alkyl sulfosuccinate, polyoxyethylene alkyl sulfate, aryl sulfonate, etc.), and cationic surfactants (alkyl amines, polyoxyethylene alkyl amines, Quaternary ammonium salts, etc.), amphoteric surfactants (such as alkylaminoethylglycine and alkyldimethylbetaine), polyhydric alcohol esters, and sugar alcohol derivatives.

Examples of fixing agents and dispersing agents include casein, gelatin, polysaccharides (starch, gum arabic, gum tragacanth,
Xanthan gum, cellulose derivatives, alginic acid, etc.),
Lignin derivatives, bentonite, saccharides, synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, etc.) and the like.
PAP (isopropyl acid phosphate), BHT (2,6-di-
tert-butyl-4-methylphenol), BHA (2-tert
-Butyl-4-methoxyphenol and 3-tert-butyl-4-
Mixtures thereof with methoxyphenol), vegetable oils, mineral oils, fatty acids or esters thereof, and the like.

The agricultural / horticultural fungicide composition of the present invention is applied to a plant or soil as it is or after dilution with water or the like. In the case of soil application, it may be sprayed on the soil surface or mixed with the soil and applied. It can also be applied by various methods such as seed treatment and ULV. When used as a seed treating agent, it is used for seed dressing treatment, seed dipping treatment, seed spraying treatment and the like.

Further, other fungicides, insecticides, acaricides,
It can also be used in combination with nematicides, herbicides, plant growth regulators, seed disinfectants, fertilizers, soil conditioners, and the like.

The application rate of the fungicidal composition for agricultural and horticultural use of the present invention varies depending on the kind of the active ingredient compound, the mixing ratio, the weather condition, the preparation form, the application time, the method, the place, the target disease, the target crop and the like. The total amount of the compounds (I) and (II), which are the active ingredients, is usually 0.001 to 1 per are.
It is 1000 g, preferably 0.1 to 100 g. When the emulsion, wettable powder, suspension, liquid preparation, etc. is diluted with water and applied, the application concentration is usually 0.0001 to 1% by weight, preferably 0 to 1% by weight. 0.0001 to 0.5% by weight, and granules, dusts and the like are applied without dilution. In seed treatment, the total amount of the active ingredient compound is usually 0.001 to 50 g, preferably 0.01 to 10 g, per 1 kg of seed.

[0060]

EXAMPLES The present invention will be described in more detail with reference to formulation examples and test examples, but the present invention is not limited to the following examples.

(Production Example 1) Reference Production Example [Table 1 Compound N
o. Production Example 1] (5-Methyl-1,2,3-thiadiazol-4-yl) phenylmethanone (0.29 g, 1.41 mmol)
To a solution of 1) in ethanol (20 ml), hydroxylamine hydrochloride (0.20 g, 2.82 mmol) and triethylamine (0.4 ml, 2.8 mmol) were added, and 48
Heated to reflux for an hour. After concentrating the reaction solution, the residue was dissolved in ethyl acetate, washed with water, and dried over magnesium sulfate.

The solvent was distilled off, and the residue was purified by column chromatography to give (Z)-(5-methyl-1,2,3
-Thiadiazol-4-yl) phenylmethanone oxime (0.16 g) and (E)-(5-methyl-1,2,2,
3-Thiadiazol-4-yl) phenylmethanone oxime (0.04 g) was obtained.

(Z)-(5-methyl-1,2,3-thiadiazol-4-yl) phenylmethanone oxime; 1
H-NMR (CDCl 3): δ 2.54 (s, 3
H), 7.30 to 7.50 (m, 5H), 8.30 to
8.45 (brd, 1H). MS (m / e): 219 (M +). (E)-(5-methyl-1,2,3-thiadiazole-
4-Hyl) phenylmethanone oxime; 1H-NMR
(CDCl3): δ 2.67 (s, 3H), 7.35
~ 7.60 (m, 5H), 8.00 to 8.20 (br
d, 1H). MS (m / e): 219 (M +).

Next, (Z)-(5-methyl-1,2,3
-Thiadiazol-4-yl) phenylmethanone oxime (9.31 g, 0.04 mol) was dissolved in acetonitrile (677 ml), and potassium carbonate (9.98 g,
0.07 mol) and the hydrochloride of 2-picolyl chloride (10.40 g, 0.06 mol) were added, and the mixture was stirred with heating under reflux for 5 hours. After concentrating the reaction solution, the residue was extracted with ethyl acetate, washed with water and dried over magnesium sulfate.
The solvent was distilled off, the residue was purified by column chromatography, and (Z)-(5-methyl-1,2,3-thiadiazol-4-yl) phenylmethanone O- (2-pyridyl) methyloxime ( 9.67 g) (Compound No. 1) was obtained.

1H-NMR (CDCl3): δ 2.5
3 (s, 3H), 5.40 (s, 2H), 7.19 (d
d, J = 4.9 Hz, J = 7.6 Hz, 1H), 7.3
0 to 7.42 (m, 3H), 7.35 (d, J = 7.8
Hz, 1H), 7.44 to 7.50 (m, 2H), 7.
7. 67 (J = 7.8 Hz, J = 7.6 Hz, 1H);
56 (d, J = 4.9 Hz, 1H). MS (m / e): 310 (M +).

(Production Example 2) Reference Production Example [Table 1 Compound N
o. Production Example 2] (3-Methyl-1,2,5-thiadiazol-4-yl) phenylmethanone (3.22 g, 15.7 mmol)
To a solution of l) in ethanol (85 ml) were added hydroxylamine hydrochloride (4.48 g, 63.1 mmol) and triethylamine (8.8 ml, 63.1 mmol), and 8
Heated to reflux for an hour.

After concentrating the reaction solution, ethyl acetate / water was added to the residue and extracted. After drying over magnesium sulfate, the solvent was distilled off. The residue was purified by column chromatography to obtain (Z)-(3-methyl-1,2,5-thiadiazol-4-yl) phenylmethanone oxime (2.18 g).

1H-NMR (CDCl3): δ 2.5
3 (s, 3H), 7.27 to 7.56 (m, 5H),
8.52 to 8.78 (brd, 1H). MS (m / e): 219 (M +).

To DMF (150 ml) was added 60% sodium hydride (2.41 g, 60.0 mmol), and the mixture was ice-cooled, and (Z)-(3-methyl-1,2,5-thiadiazol-4-yl) ) Phenylmethanone oxime (6.0
g, 27.0 mmol) and stirred for 40 minutes. To this reaction solution was added 4-chloromethyl-2-iso-propionylaminothiazole (7.76 g, 35.6 mmol).
Of DMF (110 ml) was added dropwise. The reaction solution was gradually returned to room temperature and then stirred for 20 hours. The solvent was distilled off from the reaction solution under reduced pressure, and ethyl acetate / water was added to the residue.
Extracted.

The extract was washed with water and dried over magnesium sulfate. The solvent was distilled off, the residue was purified by column chromatography, and (Z)-(3-methyl-1,2,5-thiadiazol-4-yl) phenylmethanone O- (2-
Iso-propionylaminothiazol-4-yl) methyl oxime (9.08 g) was obtained (Compound No. 2).

1H-NMR (CDCl3): δ 1.2
2 (d, J = 6.91 Hz, 6H), 2.41 (s, 3
H), 2.47 to 2.76 (m, 1H), 5.21.
(S, 2H), 6.89 (s, 1H), 7.28-7.
60 (m, 5H), 9.50 to 9.90 (brd, 1
H). MS (m / e): 401 (M +).

(Production Example 3) Reference Production Example [Table 1 Compound N
o. Production Example 3] In DMF (6 ml), 60% sodium hydride (31 m
g, 0.77 mmol), and ice-cooled to give (Z)-(3
-Methyl-1,2,5-thiadiazol-4-yl) phenylmethanone oxime (142 mg, 0.65 mmol)
l) was added and stirred for 40 minutes. To this reaction solution was added 4-chloromethyl-2-t-butyroylaminothiazole (30
(0 mg, 1.29 mmol) in DMF (6 ml) was added dropwise.

The reaction solution was gradually warmed to room temperature and then stirred for 3 days. The solvent was distilled off from the reaction solution under reduced pressure, and the residue was extracted with ethyl acetate / water. The extract was washed with water and dried over magnesium sulfate. The solvent was distilled off, the residue was purified by column chromatography, and (Z)-(3-methyl-1,2,5-thiadiazol-4-yl) phenylmethanone O- (2-t-butyroylamino Thiazol-4-yl) methyl oxime (61 mg) was obtained (Compound No. 3).

1H-NMR (CDCl3): δ 1.3
2 (s, 9H), 2.44 (s, 3H), 5.22
(S, 2H), 6.88 (s, 1H), 7.28-7.
59 (m, 5H), 8.86-9.09 (brd, 1
H). MS (m / e): 415 (M +).

(Production Example 4) Reference Production Example [Table 1 Compound N
o. Production Example 4] (5-Methyl-1,2,3-thiadiazol-4-yl)-(3-chlorophenyl) methanone (0.45 g,
1.9 mmol), hydroxylamine hydrochloride (0.32
g, 4.6 mmol) in pyridine (8 ml),
The mixture was heated and stirred in a 70 ° C. oil bath for 6.5 hours. The reaction solution was concentrated under reduced pressure, and the obtained residue was extracted with diluted hydrochloric acid-ethyl acetate. The organic layer was washed sequentially with diluted hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate and saturated saline, and then dried over magnesium sulfate.

The organic layer was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography to obtain (Z)-
(5-methyl-1,2,3-thiadiazol-4-yl)-(3-chlorophenyl) methanone oxime (29
2 mg) and (E) -5-methyl-1,2,3-thiadiazol-4-yl)-(3-chlorophenyl) methanone oxime (155 mg).

(Z)-(5-methyl-1,2,3-thiadiazol-4-yl)-(3-chlorophenyl) methanone oxime; 1H-NMR (CDCl3): δ2.5
8 (s, 3H), 7.25 to 7.45 (m, 3H),
7.51 (m, 1H), 8.08 (brd, 1H). MS (m / e): 253 (M +).

(E) -5-Methyl-1,2,3-thiadiazol-4-yl)-(3-chlorophenyl) methanone oxime; 1H-NMR (CDCl3): δ 2.73
(S, 3H), 7.35 to 7.5 (m, 3H), 7.5
4 (m, 1H), 7.80 (brd, 1H). MS (mz): 253 (M +).

(Z)-(5-Methyl-1,2,3-thiadiazol-4-yl)-(3-chlorophenyl) methanone oxime (115 mg, 0.4 ml) was added to DMF (3 ml).
5 mmol), 4-chloromethyl-2-iso-propionylaminothiazole (124 mg, 0.57 mmol)
l) was dissolved and cooled on ice. To this solution was added 60% sodium hydride (41 mg, 1.0 mmol), and the mixture was stirred at room temperature for 2.5 hours.

The reaction solution was poured into saturated aqueous ammonium chloride,
Extracted with ethyl acetate. The organic layer was washed sequentially with water and saturated saline, and dried over magnesium sulfate. The organic layer was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography to give (Z)-(5-methyl-1,2,3-thiadiazol-4-yl)-(3-chlorophenyl) methanone O- (2-iso-propionylaminothiazol-4-yl) methyl oxime (100 mg) was obtained (Compound No. 4).

1H-NMR (CDCl3): δ 1.26
(D, J = 6.8 Hz, 6H), 2.47 (s, 3
H), 2.61 (seq, J = 6.8 Hz, 1H),
5.25 (s, 2H), 6.90 (s, 1H), 7.2
5 to 7.40 Hz (m, 3H), 7.50 (m, 1
H). MS (m / z): 435 (M +).

(Production Example 5) Reference Production Example [Table 1 Compound N
o. Production Example 5] In THF (6 ml), 60% sodium hydride (44 m
g, 1.1 mmol), and ice-cooled.
Methyl-1,2,5-thiadiazol-4-yl) phenylmethanone oxime (100 mg, 0.46 mmol)
l) was added and stirred for 20 minutes. 4-Chloromethyl-2-formylaminothiazole (96 mg,
0.55 mmol) in THF (3 ml) was added dropwise. The reaction solution was gradually returned to room temperature and then stirred for 3 days. The solvent was distilled off from the reaction solution under reduced pressure, and the residue was extracted with ethyl acetate / water. The extract was washed with water and dried over magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography to give (Z)-(3-methyl-
1,2,5-thiadiazol-4-yl) phenylmethanone O- (2-formylaminothiazol-4-yl)
Methyl oxime (101 mg) was obtained.

1H-NMR (CDCl3): δ 2.2
7 (s, 3H), 5.21 (s, 2H), 6.97
(S, 1H), 7.31 to 7.52 [m, 5H], 8.
39 (s, 1H).

The above reaction product (3.42 g, 9.5 mm
ol) with methanol (70 ml) and THF (60 ml)
And cooled to 5 ° C. After adding concentrated hydrochloric acid (1.3 ml), the mixture was returned to room temperature and stirred for 20 hours. The reaction solution was concentrated, hexane was added to the residue, and the mixture was stirred. The precipitate was filtered and washed with hexane. Air-dried to give (Z)-(3-methyl-1,2,5-thiadiazole-) as colorless crystals.
4-yl) phenylmethanone O- (2-aminothiazol-4-yl) methyl oxime (3.33 g) was obtained.

1H-NMR (CDCl3): δ 2.4
1 (s, 3H), 5.06 (s, 1H), 6.85
(S, 1H), 7.30 to 7.62 [m, 5H].

The above reaction product (0.15 g, 0.41 m
mol) was dissolved in dichloromethane (15 ml), and N,
O-bis (trimethylsilyl) acetamide (0.2 m
1,0.9 mmol) and stirred for 30 minutes. This reaction solution was added to isopropyl chloroformate (0.07 ml, 0.1 mL).
5 mmol was added and the mixture was stirred for 4 days. Water was added to the reaction solution, then an aqueous solution of sodium hydrogen carbonate was added, and the mixture was extracted with ethyl acetate. After washing with water, the extract was dried over magnesium sulfate and concentrated. The residue was purified by column chromatography,
(Z)-(3-methyl-1,2,5-thiadiazole-
4-yl) phenylmethanone O- (2-isopropoxyaminothiazol-4-yl) methyl oxime (0.
135 g) (Compound No. 5).

1H-NMR (CDCl3): δ 1.3
2 (d, J = 6.22z, 6H), 2.40 (s, 3
H), 4.95-5.19 (m, 1H), 5.24.
(S, 2H), 5.24 (s, 2H), 6.81 (s,
1H), 7.30 to 7.52 [m, 5H]. MS (m / e): 417 (M +).

(Production Example 6) Reference Production Example [Table 1 Compound N
o. Production Example 6] In DMF (6 ml), 60% sodium hydride (45 m
g, 1.1 mmol), and ice-cooled to give (Z)-(5-
Methyl-1,2,3-thiadiazol-4-yl) 3-
Chlorophenylmethanone oxime (91 mg, 0.36
mmol) and stirred for 30 minutes. 4
-Chloromethyl-2-iso-valerylaminothiazole (93 mg, 0.40 mmol) in DMF (6 ml)
The solution was added dropwise.

The reaction solution was gradually warmed to room temperature and then stirred for 20 hours. The solvent was distilled off from the reaction solution under reduced pressure, and the residue was extracted with ethyl acetate / water. After the extract is washed with water,
Dried over magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography to give (Z)-(5-methyl-1,2,3-thiadiazol-4-yl) 3-chlorophenylmethanone O- (2-iso-vale). Rylaminothiazol-4-yl) methyl oxime (110 m
g) (Compound No. 6) was obtained.

1H-NMR (CDCl3): δ 0.9
9 (d, J = 6.4 Hz, 6H), 2.0 to 2.45
(M, 1H), 2.30 (d, J = 6.4 Hz, 2
H), 2.47 (s, 3H), 5.25 (s, 2H),
6.90 (s, 1H), 7.25 to 7.45 (m, 4
H), 9.29 (brd, 1H). MS (m / e): 449 (M +).

(Production Example 7) Reference Production Example [Table 1 Compound N
o. Production Example 7] (Z)-(3-methyl-1,2,5-thiadiazole-
4-yl) phenylmethanone To a solution of O- (2-phenyloxycarbonylaminothiazol-4-yl) methyl oxime (30 mg, 0.066 mmol) in dimethylsulfoxide (3.5 ml_) was added 40% dimethylamine (30 μl). The mixture was stirred at room temperature for 2 hours. Ethyl acetate was added to the reaction solution, and then washed sequentially with water, 2N hydrochloric acid, and 1% aqueous sodium hydroxide. The ethyl acetate extract was dried over magnesium sulfate and concentrated. The residue was purified by column chromatography, and (Z)-(3-methyl-
1,2,5-thiadiazol-4-yl) phenylmethanone O- [2- (N ', N'-dimethylureido) thiazol-4-yl] methyloxime (30 mg) was obtained (Compound No. 7). .

1H-NMR (CDCl3): δ 2.4
1 (s, 3H), 3.04 (s, 3H), 5.18
(S, 2H), 6.77 (s, 1H), 7.28-7.
52 [m, 5H]. MS (m / e): 401 (M +).

(Production Example 8) Reference Production Example [Table 1 Compound N
o. Production Example 8] In DMF (6 ml), 60% sodium hydride (80 m
g, 2 mmol), and ice-cooled. (Z)-(3-Methyl-1,2,5-oxadiazol-4-yl) 4-fluorophenylmethanone oxime (80 mg, 0.36
mmol) and stirred for 30 minutes. 4
-Chloromethyl-2-iso-propionylaminothiazole (100 mg, 0.43 mmol) in DMF (6
ml) solution was added dropwise. The reaction solution was gradually returned to room temperature and then stirred for 20 hours. The solvent was distilled off from the reaction solution under reduced pressure, and the residue was extracted with ethyl acetate / water.

The extract was washed with water and dried over magnesium sulfate. The solvent was distilled off and the residue was purified by column chromatography to give (Z)-(3-methyl-1,2,5-oxadiazol-4-yl) 4-fluorophenylmethanone O- (2- Iso-propionylaminothiazol-4-yl) methyl oxime (107 mg) was obtained (Compound No. 8).

1H-NMR (CDCl3): δ 1.0
0 (d, J = 6.23 Hz, 6H), 2.07 to 2.4
5 (m, 1), 2.28 (s, 3H), 5.24 (s,
2H), 6.90 (s, 1H), 6.96 to 7.18.
(M, 2H), 7.42 to 7.68 (m, 2H), 8.
82-9.14 (brd, 1H). MS (m / e): 417 (M +).

(Production Example 9) Reference Production Example [Table 1 Compound N
o. Production Example 9] (Z)-(3-Methyl-1,2,5-oxadiazol-4-yl) 3-fluorophenylmethanone oxime (173 mg, 0.78 mmol) was dissolved in acetonitrile (20 ml), Potassium carbonate (184 mg,
1.33 mmol) and 2-picolyl chloride (23
6 mg, 1.42 mmol), and the mixture was stirred with heating under reflux for 6 hours. After concentrating the reaction solution, the residue was extracted with ethyl acetate, washed with water and dried over magnesium sulfate. The solvent was distilled off and the residue was purified by column chromatography,
(Z)-(3-methyl-1,2,5-oxadiazol-4-yl) 3-fluorophenylmethanone O- (2
-Pyridyl) methyl oxime (155 mg) was obtained (Compound No. 9).

1H-NMR (CDCl3): δ 2.3
2 (s, 3H), 5.41 (s, 2H), 6.98-
7.48 (m, 6H), 7.70 (t, J = 7.63H)
z, 1H), 8.59 (d, J = 4.81 Hz, 1
H). MS (m / e): 312 (M +).

(Production Example 10) Reference Production Example [Table 1 Compound No. Production Example 10] 60% sodium hydride (53 mg, 1.3 mmol) was added to dimethylformamide (6 ml), and the mixture was ice-cooled.
(Z)-(3-Methyl-1,2,5-oxadiazol-4-yl) 4-fluorophenylmethanone oxime (100 mg, 0.46 mmol) was added, and the mixture was stirred for 30 minutes. 4-Chloromethyl-2-t-butyroylaminothiazole (128 mg, 0.55 mmol) was added to the reaction mixture.
A solution of l) in dimethylformamide (6 ml) was added dropwise.

The reaction solution was gradually warmed to room temperature and then stirred for 3 days. The solvent was distilled off from the reaction solution under reduced pressure, and the residue was extracted with ethyl acetate / water. The extract was washed with water and dried over magnesium sulfate. The solvent was distilled off, the residue was purified by column chromatography, and (Z)-(3-methyl-1,2,5-thiadiazol-4-yl) phenylmethanone O- (2-t-butyroylamino Thiazol-4-yl) methyl oxime (138 mg) was obtained.
(Compound No. 10)

1H-NMR (CDCl3): δ 1.3
3 (s, 9H), 2.30 (s, 3H), 5.24
(S, 2H), 6.91 (s, 1H), 6.99-7.
16 [m, 2H], 7.43 to 7.69 (m, 2H),
8.72 to 9.00 (brd, 1H). MS (m / e): 417 (M +).

(Formulation Example 1) Compound Nos. 1 to 10 (20 parts by weight) obtained in Production Examples 1 to 10 were added to clay (6
8 parts by weight), white carbon (8 parts by weight), and polyoxyethylene nonylphenyl ether (4 parts by weight) were sufficiently pulverized and mixed to obtain a wettable powder.

(Formulation Example 2) Metalaxyl was used as a metalaxyl standard product (a reagent manufactured by Kanto Chemical Co., Ltd.) (20 parts by weight)
Clay (68 parts by weight), white carbon (8 parts by weight), polyoxyethylene nonyl phenyl ether (4
Parts by weight) were thoroughly pulverized and mixed to obtain a wettable powder.

(Formulation Example 3) Compound Nos. 1 to 10 (20 parts by weight) obtained in Production Examples 1 to 10 were added to a metalaxyl standard product (a reagent manufactured by Kanto Chemical Co., Ltd.) (20 parts by weight) and clay (48 parts). Parts by weight), white carbon (8 parts by weight), and polyoxyethylene nonylphenyl ether (4 parts by weight) were sufficiently pulverized and mixed to obtain a wettable powder.

(Test Example 1) A wettable powder containing a predetermined compound prepared according to the method of Preparation Example was placed in a test tube, and diluted with water to a predetermined active ingredient concentration. Three leaf disks of grapes (variety: Neo Muscat) punched with a cork borer having a diameter of 10 mm were put into this test solution. Thirty minutes later, the leaf disk was taken out and placed on a filter paper spread on a plastic petri dish with the back of the leaf facing upward.
Absorb the filter paper and remove grape downy mildew (Plasmopara viticol)
The spore suspension of a) was spray inoculated on a leaf disk. After sealing the plastic petri dish, the disease was caused in a growth cabinet (25 ° C., 5000 Lx, 14 hours, 18 ° C. dark condition, 10 hours, humidity 70%). Seven days later,
The disease incidence was investigated and the disease index was determined.

That is, “0” means no disease, and the diseased area is 2
If the diseased area is 25% or more and less than 50% is "1", the diseased area is "2", and the diseased area is 50% or more is "3". Number of leaves x index) ÷
(Number of surveyed leaves × 5)｝ × 100 ”. The control value is

[0106]

(Equation 1)

Calculated using Here, P: control value (%) A: disease degree of untreated plant (%) B: disease degree of treated plant (%)

Further, the expected value of the control value was calculated using the following equation: E = M + N-MN / 100.

E: Expected control value (%) M: Control value (%) when compound (I) is used alone N: Control value (%) when compound (II) is used alone The results are shown in Tables 3 and 4.

[0110]

[Table 3]

[0111]

[Table 4]

[0112]

According to the present invention, it is possible to provide a novel agricultural / horticultural fungicide composition having an excellent control effect on plant diseases. More specifically, a novel agricultural and horticultural fungicide composition exhibiting an excellent effect of controlling a wide range of crop diseases under aggressive conditions, particularly plant diseases caused by algae, and the agricultural and horticultural fungicide composition, A method for controlling plant diseases, particularly plant diseases caused by algae, can be provided.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Jin Kondo 1-25-16- 205, Chijodaihigashi, Wakaba-ku, Chiba-shi, Chiba Prefecture Terms (reference) 4C063 AA01 BB07 CC58 CC67 DD12 DD62 EE03 4H011 AA01 BA01 BA06 BB06 BB10 BC18 BC19 BC20 DA15 DC03 DC05 DD03 DH02 DH03

Claims (7)

[Claims] 1. The following general formula (1): [However, HetA is represented by the following two formulas. (Wherein R ¹ is a hydrogen atom, a lower alkyl group, an amino group,
Or an alkoxy group. HetB is a group represented by any one of the following three formulas: (Wherein, Y represents a lower alkyl group), and HetC is a group represented by the following formula: (Wherein, X is a halogen atom, and n is 0 to 3.)] and an RNA synthesis-inhibiting bactericidal compound (II) as active ingredients. A fungicidal composition for agricultural and horticultural use. 2. In the general formula (1), R ¹ is a propyl group, a butyl group, an amino group, or a propoxy group;
Is a methyl group, and X is a hydrogen atom, a fluorine atom or a chlorine atom, The agricultural / horticultural fungicide composition of Claim 1. 3. The bactericidal compound (II) for inhibiting RNA synthesis is an anilide compound.
The fungicidal composition for agricultural and horticultural use according to 1. 4. The fungicidal composition for agricultural and horticultural use according to claim 3, wherein the anilide-based compound is at least one compound selected from metalaxyl, benalaxyl, furalaxyl, offrace, oxadixyl, and ciprofram. object. 5. The method according to claim 5, wherein the oxime derivative (I) and the RNA synthesis-inhibiting fungicidal compound (II) are (I) / (II) = 0.1 / 99.
The fungicide composition for agricultural and horticultural use according to any one of claims 1 to 4, wherein the composition is 9 to 99.9 / 0.1 (weight ratio). 6. A method for controlling plant diseases using the fungicide composition for agricultural and horticultural use according to any one of claims 1 to 5. 7. The control method according to claim 6, wherein the plant disease is a plant disease derived from algae.