WO2007029793A1

WO2007029793A1 - Aryl heterocyclic derivative and bactericide for agricultural and horticultural use

Info

Publication number: WO2007029793A1
Application number: PCT/JP2006/317792
Authority: WO
Inventors: Yoshihiko Hara; Tomoyuki Saiga
Original assignee: Nippon Soda Co., Ltd.
Priority date: 2005-09-07
Filing date: 2006-09-07
Publication date: 2007-03-15
Also published as: JP2008290945A

Abstract

Disclosed is an aryl heterocyclic derivative which can be commercially advantageously synthesized and safely used as a surely effective active ingredient for bactericides for agricultural and horticultural use. Also disclosed are a salt of such a derivative and a bactericide for agricultural and horticultural use containing such a compound as an active ingredient. Specifically disclosed are an aryl heterocyclic derivative represented by the formula (1) below or a salt thereof, and a bactericide for agricultural and horticultural use containing one or more of such compounds as an active ingredient. (1) [In the formula, R1 represents a C1-6 alkyl group or the like; R2 represents a halogen atom, a C1-6 alkyl group or the like; m represents an integer of 0-4; R3 represents a halogen atom or the like; n represents an integer of 0-5; G represents an oxygen atom or a sulfur atom; A represents one of the groups represented by the formulae (2)-(4) below and Q1 represents one of the groups represented by the formulae (5)-(9) below; (wherein R4-R8 respectively represent a hydrogen atom or the like; k represents an integer of 1-4; R9 represents a hydrogen atom, a halogen atom or the like; E represents an oxygen atom or a sulfur atom; and g represents an integer of 0-3); Q2 represents a phenyl group or the like; R10 represents a chemically acceptable arbitrary substituent; and l represents an integer of 0-4.]

Description

Aryl heterocyclic derivatives and agricultural and horticultural fungicides

Technical field

[0001] The present invention relates to novel aryl derivatives or salts thereof, and agricultural and horticultural fungicides containing these as active ingredients.

This application claims priority based on Japanese Patent Application No. 2005-259176 filed in Japan on September 7, 2005, the contents of which are incorporated herein by reference.

Background art

[0002] In the cultivation of agricultural and horticultural crops, many control agents are used against crop diseases. Their control efficacy is insufficient, or their use is restricted by the emergence of drug-resistant pathogens. In addition, there are many things that are not necessarily satisfactory control drugs from the viewpoint of causing phytotoxicity and pollution to plants, or from the viewpoint of toxicity to human and livestock fish and environmental impact. Therefore, there is a strong demand for the emergence of drugs that can be used safely and have few drawbacks.

[0003] In relation to the present invention, Patent Document 1 and the like disclose that a compound represented by the following formula has a bactericidal activity, but ^Ra and ^Rb together form a ring. The compounds are not described.

[0004] [Chemical 1]

(In the formula, A ′ represents —NHNH—, G ′ represents an oxygen atom, X, Y represents a halogen atom, R ^a and R ^b represent an alkyl group, and R ^e represents an alkyl group, an alkoxy group, etc. Q ′ represents a heterocyclic group, m, represents an integer of 0 to 4, and n ′ represents an integer of 0 to 5.

Patent Document 1: WO2005Z051932 Pamphlet Disclosure of the invention

Problems to be solved by the invention

[0006] The present invention is effective for allylic heterocyclic derivatives and salts thereof, which can be synthesized industrially advantageously, have reliable effects and can be used safely, and can be used as active ingredients for agricultural and horticultural fungicides, and their compounds. An object is to provide an agricultural and horticultural fungicide as an ingredient.

Means for solving the problem

[0007] In the present invention, firstly, the formula (1)

[0008] [Chemical 2]

[Wherein, R ¹ represents a C alkyl group or a C alkoxy group.

1-6 1-6

R ² is a halogen atom, C alkyl group, C alkoxy group, C hydroxyalkyl

1-6 1-6 1-6

Group, C alkyloxy C alkyl group, or C alkylcarboxoxy

1-6 1-6 1-6

C represents an alkyl group.

1-6

m represents an integer of 0-4. When m is 2 or more, R ² may be the same or different.

R ³ is a halogen atom, C alkyl group, C alkoxy group, C hydroxyalkyl

1-6 1-6 1-6

Group, C alkyloxy C alkyl group, or C alkylcarboxoxy

1-6 1-6 1-6

C represents an alkyl group.

1-6

n represents an integer of 0 to 5. When n is 2 or more, R ³ may be the same or different.

G represents an oxygen atom or a sulfur atom.

A represents a group represented by the following formulas (2) to (4)! /.

[0010] [Chemical 3] R ⁴ R ⁵

( ²⁾

R ⁶

R ⁷ R ⁸

—— N— —— ⁽³⁾

—— = N— (4)

[Wherein R ⁴ and R ⁷ are each independently a hydrogen atom, C alkyl group, C alkyl

1-6 1-6 represents a carbo group or a C haloalkyl carbo group.

1-6

RR ⁶ and R ⁸ each independently represents a hydrogen atom or a C alkyl group.

1-6

k represents an integer of 1 to 4. When k is 2 or more, groups represented by the formula: —C (R ⁴ ) (R ⁶ ) — may be the same or different. )

Q ¹ is represented by the following formulas (5) to (9)! /, Which represents any group.

[0012] [Chemical 4]

, N,

II (6)

J,

\\ (7)

N-E

[In the formula, R ⁹ represents a hydrogen atom, a halogen atom, a C alkyl group, or a C alkyl

1 -6 1 -6

Represents a bonyl group, E represents an oxygen atom or a sulfur atom, and g represents an integer of 0 to 3. Q ² represents a phenol group or an aromatic heterocyclic ring.

R ^1Q represents any substituent that is chemically acceptable.

1 represents an integer from 0 to 4. When 1 is 2 or more, R ^1Q may be the same or different. ]

And a salt thereof.

Secondly, the present invention provides an agricultural and horticultural fungicide containing, as an active ingredient, one or more of the aryl heterocyclic derivatives represented by the formula (1) or salts thereof.

The invention's effect

[0014] According to the present invention, a novel aryl derivative or a salt thereof having an excellent control effect for controlling diseases of useful plants, and one or more of these as an active ingredient An agricultural and horticultural fungicide is provided. BEST MODE FOR CARRYING OUT THE INVENTION

[0015] 1) Aryl heterocyclic derivatives and salts thereof

A first aspect of the present invention is an aryl heterocyclic derivative represented by the formula (1) (hereinafter sometimes referred to as “aryl heterocyclic derivative (1)”) and a salt thereof.

In the above formula (1), R ¹ is a C alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec butyl group, an isobutyl group, or a t-butyl group; Or

1 -6

Represents a C alkoxy group such as a toxi group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec butoxy group, an isobutoxy group, and a t-butoxy group.

1 -6

[0017] R ² is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a methyl group, an ethyl group, an n propyl group, an isopropyl group, an n butyl group, a sec butyl group, an isopropyl group, t- C alkyl group such as butyl group; C alkoxy such as methoxy group and ethoxy group

1 -6 1 -6 group; C hydride such as hydroxymethyl group, 1 hydroxyethyl group, 2-hydroxyethyl group

1-6 loxyalkyl group; C alkyloxy C alkyl group such as methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 2-methoxystyl group; or acetoxymethyl group,

1 -6 1-6

C-alkyl such as propoxymethyl group, 1-acetoxetyl group, 2-acetoxetyl group

1 -6 cycloalkyl-alkyloxy alkyl group;

1 -6

[0018] m represents an integer of 0 to 4. When m is 2 or more, R ² may be the same or different.

[0019] R ³ represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a methyl group, an ethyl group, an n propyl group, an isopropyl group, an n butyl group, a sec butyl group, an isopropyl group, t- C alkyl group such as butyl group; C alkoxy such as methoxy group and ethoxy group

1 -6 1-6

C-alkyl such as propoxymethyl group, 1-acetoxetyl group, 2-acetoxetyl group

1 -6 cycloalkyl-alkyloxy alkyl group;

1 -6

[0020] n represents an integer of 0 to 5. When n is 2 or more, R ³ may be the same or different. G represents an oxygen atom or a sulfur atom.

[0021] A represents a group of! / Represented by the above formulas (2) to (4).

In formulas (2) and (3), R ⁴ and R ⁷ are each independently a hydrogen atom; methyl group, ethyl group, n-propyl group, isopropyl group, n butyl group, sec butyl group, isobutyl group, t C alkyl group such as butyl group; acetyl group, propionyl group, butylyl group, isoptylyl group

1 -6

C alkylcarbonyl group such as difluoroacetyl group, trifluoroacetyl group, etc.

1 -6

A C haloalkylcarbonyl group such as a group;

1 -6

In the above formula (2), R ⁵ , R ⁶ and R ⁸ are each independently a hydrogen atom; or a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n butyl group, a sec butyl A C alkyl group such as a group, isobutyl group, t-butyl group;

1 -6

[0023] k represents an integer of 1 to 4. When k is 2 or more, the groups represented by the formula: C (R ⁴ ) (R ⁶ ) — may be the same or different from each other.

[0024] Q ¹ is represented by the above formula (5) to (9), represents a group of Zureka.

In formulas (5) to (9), R ⁹ is a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a methyl group, an ethyl group, an n propyl group, an isopropyl group, an n butyl group, sec C alkyl group such as butyl group, isobutyl group, t-butyl group; or acetyl

1 -6

A C alkyl carbonyl group such as a group, propiol group, butyryl group, isobutyryl group;

1 -6

To express.

E represents an oxygen atom or a sulfur atom.

G represents an integer of 0 to 3.

Q ¹ represents a phenyl group or an aromatic heterocyclic ring such as a pyridine-2-yl group, a pyridine-1-yl group, a pyridine-4-yl group, or a pyrazine 2-yl group.

Specific examples of Q ² include a phenyl group; an aromatic heterocyclic group such as a furanyl group, an imidazolyl group, an oxazolyl group, a thiazolyl group, a pyridinyl group, a pyrimidinyl group, and a birazinyl group.

R ^1C> is not limited as long as it is chemically acceptable, but for example, halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, n propyl group, isopropyl group _N- butyl group, sec-butyl group, isobutyl group, t-butyl group, etc. No. Alkyl group; c haloalkyl such as trifluoromethyl group, 1 chloroethyl group, etc.

1-6 1-6 group; c alkoxy group such as methoxy group and ethoxy group; amino group, monomethylamino group,

1 -6

Mono- or di-substituted such as a tyramino group, or an amino group;

1 represents an integer of 0 to 4. When 1 is 2 or more, R ^1Q may be the same or different.

[0025] The aryl heterocyclic derivative (1) can be produced by the production method described below.

The method for producing aryl aryl derivative (1) is not limited to these as long as it can produce aryl aryl derivative (1).

[0026] (Production method 1)

Among the aryl heterocyclic derivatives (1), as shown below, the compound represented by the formula (11) can be obtained by combining a compound represented by the formula (I) and a compound represented by the formula (II), if desired. The reaction can be carried out in the presence of.

[0027] [Chemical 5]

[0028] (where

R ³ , R ⁹ , A, G, m, and n represent the same meaning as described above. Y represents a leaving group such as a halogen atom. )

[0029] The amount of the compound represented by the formula (II) used is usually 0.5 to 5 times mol, preferably 0.7 to 2 times mol, of the compound represented by the formula (I). .

[0030] The base used in this reaction is not particularly limited. For example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; pyridine, Organic bases such as triethylamine, N, N dimethylamino, 4-dimethylaminoviridine, N-methylpyrrolidine, N-methylmorpholine, 1,8 diazabicyclo [5.4.0] undecar 7; The amount of the base used is usually 1 to 10 times mol, preferably 1 to 3 times mol, of the compound represented by the formula (I).

[0031] This reaction can be carried out in the presence or absence of a solvent.

The solvent to be used is not particularly limited as long as it is inert to the reaction. For example, hydrocarbon solvents such as pentane, hexane, heptane, benzene, toluene and xylene; dichloromethane, 1,2-dichloromethane Halogen solvents such as ethane, chloroform, carbon tetrachloride; alcohols such as methanol and ethanol; -tolyl solvents such as acetonitrile and propion-tolyl; ether solvents such as jetyl ether, dioxane and tetrahydrofuran; N , N-dimethylformamide, dimethyl sulfoxide and the like aprotic polar solvents; water; and a mixed solvent having two or more of these solvents.

[0032] The reaction temperature is usually in the range of -78 ° C to + 200 ° C, preferably -20 ° C to + 100 ° C.

The reaction time is usually 30 minutes to 100 hours, although it depends on the type of reaction reagent and reaction scale.

[0033] The compound represented by the formula (Π) can be produced, for example, by allowing a halogenating agent to act on the compound represented by the formula (III) as shown below.

[0034] [Chemical 6]

(ΠΙ) (Π)

[Wherein, R ³ , R ⁹ , n represent the same meaning as described above. Y ′ represents a halogen atom.]

The halogenating agent to be used is not particularly limited, and examples thereof include salt and thionyl bromide.

-L, sulfuryl chloride, chlorine, bromine and the like.

[0036] The compound represented by the formula (III) includes, for example, as shown below, a compound represented by the formula (IV) and a compound represented by the formula (V), optionally in the presence of a base. By reacting to

It can be manufactured.

[0037] [Chemical 7]

(IV) (Π)

(In the formula, R ³ , R ⁹ and n represent the same meaning as described above. L represents a leaving group such as a halogen atom.)

[0039] The amount of the compound represented by the formula (V) to be used is generally in the range of 1 to 5 times mol, preferably 1 to 2 times mol, of the compound represented by the formula (IV).

[0040] Examples of the base used in this reaction include organic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydride; pyridine, Organics such as triethylamine, N, N-dimethylamino, 4-dimethylaminopyridine, N-methylpyrrolidine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] undeca-7-ene Base; and the like.

The amount of the base used is usually 1 to 10 times mol, preferably 1 to 5 times mol, of the compound represented by the formula (IV).

[0041] This reaction can be performed in the presence or absence of a solvent.

The solvent used is not particularly limited as long as it is inert to the reaction. For example, hydrocarbon solvents such as pentane, hexane, heptane, benzene, toluene, xylene; dichloromethane, 1,2-dichloroethane. Halogen solvents such as chloroform, carbon tetrachloride; alcohols such as methanol and ethanol; -tolyl solvents such as acetonitrile and propion-tolyl; ether solvents such as jetyl ether, dioxane and tetrahydrofuran; N, And aprotic polar solvents such as N-dimethylformamide and dimethylsulfoxide; water; and a mixed solvent having two or more of these strengths.

[0042] The reaction temperature is usually in the range of -78 ° C to + 200 ° C, preferably -20 ° C to + 100 ° C.

[0043] (Production method 2) Among the aryl heterocyclic derivatives represented by the above formula (1), the compound represented by the formula (12) is a compound represented by the formula (VI) as shown below, if desired. It can be produced from ring closure in the presence.

[Chemical 8]

[0045] (where

R ² , R ³ , A, G, m, and n represent the same meaning as described above. )

Examples of the base used in the reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; pyridine, triethylamine, N, N dimethylaniline. , 4-dimethylaminopyridine, N-methylpyrrolidine, N-methylmorpholine, and organic bases such as 1,8 diazabicyclo [5.4.0] unde.

The amount of the base to be used is generally 0.01 to: LO times mol, preferably 0.1 to 3 times mol, with respect to the compound represented by the formula (VI).

[0046] Examples of the acid to be used include inorganic acids such as hydrochloric acid and sulfuric acid; organic acids such as trifluoroacetic acid and p-toluenesulfonic acid.

The amount of the acid to be used is generally 0.01 to: LO times mole, preferably 0.1 to 3 times moles, relative to the compound represented by the formula (VI).

[0047] This reaction can be carried out in the presence or absence of a solvent.

Solvents that can be used are not particularly limited as long as they are inert to the reaction. For example, hydrocarbon solvents such as pentane, hexane, heptane, benzene, toluene, xylene, dichloromethane, 1,2-dichloroethane, Halogen solvents such as black mouth form and carbon tetrachloride, alcohols such as methanol and ethanol, tolyl solvents such as acetonitrile and propion-tolyl, ether solvents such as jetyl ether, dioxane and tetrahydrofuran, N, N And aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide, water, and a mixed solvent composed of two or more of these solvents. [0048] The reaction temperature ranges from -78 ° C to + 200 ° C, preferably from -20 ° C to + 100 ° C. The reaction time is usually 30 minutes to 100 hours, although it depends on the type of reaction reagent and reaction scale.

[0049] The compound represented by the formula (VI) includes, for example, as shown below, a compound represented by the formula (VII) and a compound represented by the formula (VIII) in the presence of a base or a dehydrating agent as desired. It can be manufactured by making it react.

[0050] [Chemical 9]

[0051] (where

R ² , R ³ , A, G, m, and n represent the same meaning as described above. X represents a leaving group such as a hydroxyl group or a halogen atom. )

The amount of the compound represented by the formula (VIII) used is usually 1 to

The range is 5 moles, preferably 1 to 2 moles.

[0052] Examples of the base used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate; pyridine, triethylamine, 、 Organic bases such as, Ν-dimethylaline, 4-dimethylaminopyridine, Ν-methylpyrrolidine, Ν-methylmorpholine, 1,8-diazabicyclo [5.4.0] Can be mentioned.

The amount of the base used is usually 1 to 10 times mol, preferably 1 with respect to the compound represented by formula (VII).

~ 3 times mole.

[0053] Examples of the dehydrating agent include calposimides such as Ν, Ν-dicyclohexylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, and the like. As a reaction method using a dehydrating agent, Mitsunobu reaction method (for example, J. Chem. Soc., Per kin Trans I., 1708 (1976)) can also be employed.

[0054] This reaction can be carried out in the presence or absence of a solvent.

The solvent to be used is not particularly limited as long as it is inert to the reaction. For example, hydrocarbon solvents such as pentane, hexane, heptane, benzene, toluene and xylene; dichloromethane, 1,2-dichloromethane Halogen solvents such as ethane, chloroform, carbon tetrachloride; -tolyl solvents such as acetonitrile and propion-tolyl; ether solvents such as jetyl ether, dioxane and tetrahydrofuran; N, N-dimethylformamide, dimethylsulfo An aprotic polar solvent such as xoxide; water; and a mixed solvent of two or more of these solvents.

[0055] The reaction temperature ranges from −78 ° C. to + 200 ° C., preferably from −20 ° C. to + 100 ° C.

[0056] As shown below, the intermediate compound represented by the formula (VIII) is obtained by subjecting the compound represented by the formula (IX) to a known hydrolysis method, for example, in the presence of an acid such as sulfuric acid. It can be produced by a hydrolysis method.

[0057] [Chemical 10]

[In the formula, R ³ and n represent the same meaning as described above.]

The compound represented by the formula (IX) is produced, for example, by reacting a compound represented by the formula (X) and a compound represented by the formula (V) in the presence of a base as desired, as shown below. can do.

[0059] [Chemical 11]

(Wherein R ³ , n and L represent the same meaning as described above.)

The amount of the compound represented by the formula (V) to be used is generally in the range of 1 to 5 times mol, preferably 1 to 2 times mol, of the compound represented by the formula (X).

[0061] Examples of the base used in the reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride; pyridine, triethylamine, Organic bases such as N, N-dimethylamino, 4-dimethylaminopyridine, N-methylpyrrolidine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] undecar 7-en; Can be mentioned.

The amount of the base to be used is generally 1 to 10-fold mol, preferably 1 to 5-fold mol based on the compound represented by the formula (X).

[0062] This reaction can be carried out in the presence or absence of a solvent.

Solvents that can be used are not particularly limited as long as they are inert to the reaction. For example, hydrocarbon solvents such as pentane, hexane, heptane, benzene, toluene, and xylene; dichloromethane, 1,2-dichloroethane Halogen solvents such as chloroform, carbon tetrachloride; alcohol solvents such as methanol and ethanol; -tolyl solvents such as acetonitrile and propion-tolyl; ether solvents such as jetyl ether, dioxane and tetrahydrofuran; N, Aprotic polar solvents such as N-dimethylformamide and dimethyl sulfoxide; water; and a mixed solvent composed of two or more of these solvents.

[0063] The reaction temperature ranges from −78 ° C. to + 200 ° C., preferably from −20 ° C. to + 100 ° C.

[0064] The salt of the aryl heterocyclic derivative (1) is not particularly limited as long as it is an agriculturally and horticulturally acceptable salt. For example, salts of inorganic acids such as hydrochloride, nitrate, sulfate, phosphate; acetic acid And salts of organic acids such as salts, lactates, propionates and benzoates. These salts can be produced from the aryl heterocyclic derivative (1) and the corresponding acid by a conventionally known method.

[0065] In any reaction, after completion of the reaction, the target product can be isolated by a usual separation and purification means in organic synthetic chemistry.

The structure of the target product can be identified and confirmed by known analytical means such as measurement of NMR ^ vector, IR ^ vector, mass spectrum, etc., and elemental analysis.

[0066] The compound of the present invention (Aaryl heterocyclic derivative (1) or a salt thereof) obtained as described above is used for a wide variety of filamentous fungi, such as oomycetes, gonococcal fungi ( Asc omycetes), Ungenzen! (Deuteromycetes), Tana | | (Basidiomycetes) Therefore, the composition containing the compound of the present invention as an active ingredient is used by seed treatment, foliage application, soil application or water surface application, etc. can do.

[0067] Examples of diseases in which the compound of the present invention is effective include the following.

Sugar beet (Cercospora beticola)

Mycosphaerella arachidis

Kuroshibu ί 丙 (Mycosphaerella berkeleyi)

Cucumber tsudondon;) 丙 (Sphaerotheca fuliginea)

Tsuru withered (Mycosphaerella meionis)

Mycorrhizal ί 丙 (Scierotmia sclerotiorum)

Gray rickets (Botrytis cinerea)

Black Star ί 丙 (Ciadosporium cucumerinum

Botrytis cinerea

Force, gonorrhea (Ciadosporium fulvum)

Eggplant gray mold (Botrytis cinerea)

Black fold disease (Corynespora meiongenae)

Tsudonko;) 丙 (Erysiphe cichoracearum)

Strawberry Gray mold disease (Botrytis cinerea) Powdery mildew (Sohaerotheca humuli)

Onion gray rot (Botrytis allii)

Gray rickets (Botrytis cinerea)

Kidney sclerotia (Sclerotinia sclerotiorum)

Gray power, gonorrhea (Botrytis cinerea)

Rinko tsudonoko disease (Podosphaera leucotricha)

Black star disease (Venturia inaequalis)

Monilinia mali

Oyster powdery mildew (Phyllactinia kakicola)

Anthracite (Gloeosporium Kaki

Spotted leaf disease (Cercospora kaki)

Peach 'Otou' ash scab (Monilinia fructicola;

Grape gray mold (Botrytis cinerea)

Tsudonko disease (Uncinula necator)

Rot (Glomerella cingulata)

Pear black star;) 丙 (Venturia nashicola)

Red nose (Gymnosporangium asiaticum) Black spot (Alternaria kikuchiana)

Chia ring spot disease (Pestalotia theae)

Anthracnose (Colletotrichum theae― sinensis) Kanki scab (Elsinoe fawcetti)

Blue Rust (Penicillium italicum)

Green power (Penicillium digitatum)

Gray force pattern (Botrytis cinereaj

Omugi powdery mildew (Erysiphe graminis f. Sp. Hordei;

Bare Scab (Ustilago nuda)

Wheat red blight (Gibberella zeae)

Red rust pattern (Puccinia recondita) Spot disease (Cochliobolus sativus)

to sentence disease (Pseudocercosporella herpotrichoides)

Blight (Leptosphaeria nodorum)

Powdery mildew (Erysiphe graminis f. Sp. Tritici)

Scarlet snow rot (Micronectriella nivalis)

[0069] Rice Blast (Pyricularia oryzae)

Rhizoctonia solan

Idiot Seedling (Gibberella fujikuroi)

¾leaves; * 丙 (Cochliobolus niyabeanus

Tobacco sclerotia (Sclerotinia sclerotiorum

Tsutenkoko (Erysiphe cichoracearum)

Tulip Gray mold (Botrytis cinerea)

Bentgrass, Snow rot, Mycobacterium tuberculosis (Sclerotinia borealis)

Orchard Goubs, powdery mildew (Erysiphe graminis)

Thais Purpura (Cercospora kikuchii

Potato 'Tomato Blight (Phytophthora infestans)

Cucumber toto ί 丙 (Pseudoperonospora cubensis)

Grapes and!丙 (Plasmopara viticola)

It can be used for the control of etc.

[0070] Also, in recent years, various pathogenic bacteria have developed resistance to les, benzimidazole fungicides, dicarboxyimide fungicides, etc., resulting in insufficient efficacy of these drugs. An effective drug is desired. The compound of the present invention is a drug having an excellent bactericidal effect not only on pathogenic bacteria sensitive to these drugs but also on resistant bacteria.

[0071] For example, Botrytis cinerea, Cercospora beticola, Venturia inaequalis, pear, and pear that are resistant to benzimidazole fungicides such as thiophanate methyl, benomyl, and carbendazim The compound of the present invention is also effective against Venturia nashicola) as is the case with susceptible bacteria.

[0072] Further, dicarboximide fungicides (for example, vinclozoline, procymidone, diplodi The compound of the present invention is also effective against Botrytis cinerea which is resistant to ON), as is the case with susceptible bacteria.

[0073] Examples of diseases that can be applied more preferably include sugar beet brown spot, wheat powdery mildew, rice blast, apple black scab, cucumber gray mold, and peanut brown spot.

[0074] The compound of the present invention is a highly safe drug with low toxicity to fish and warm-blooded animals with less phytotoxicity.

[0075] 2) Agricultural and horticultural fungicides

The agricultural and horticultural fungicide of the present invention is characterized by containing one or more of the compounds of the present invention as an active ingredient.

[0076] The agricultural and horticultural fungicide of the present invention may contain one or two or more of the compounds of the present invention in a pure form without any other components, and is generally used for the purpose of use as an agricultural chemical. It may be in the form of agricultural chemicals, that is, in the form of wettable powder, granule, powder, emulsion, aqueous solvent, suspension, granular wettable powder and the like.

[0077] Additives and carriers that can be added to agricultural chemical formulations include solid powders, vegetable powders such as soybean flour and wheat flour, diatomaceous earth, apatite, gypsum, talc, bentonite, Examples include mineral fine powders such as pyrophyllite and clay, and organic and inorganic compounds such as sodium benzoate, urea, and sodium sulfate.

[0078] When the liquid dosage form is intended, kerosene, xylene and petroleum aromatic hydrocarbons, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, trichlor. Ethylene, methyl isobutyl ketone, mineral oil, plant oil, water, etc. can be used as solvents.

[0079] Further, in order to obtain a uniform and stable form in these preparations, a surfactant may be added as necessary.

The surfactant that can be added is not particularly limited. For example, alkylphenyl ether with polyoxyethylene attached, alkyl ether with polyoxyethylene attached, higher fatty acid ester with polyoxyethylene added. , Non-ionic surfactants such as sorbitan higher fatty acid ester added with polyoxyethylene, tristyryl ether added with polyoxyethylene, polyoxyethylene added Lucyl sulfate ether sulfate, alkyl benzene sulfonate, higher alcohol sulfate, alkyl naphthalene sulfonate, polycarboxylate, ligno sulfonate, formaldehyde condensate of alkyl naphthalene sulfonate, isobutylene maleic anhydride An acid copolymer etc. are mentioned.

[0080] The wettable powder, emulsion, flowable powder, aqueous solvent, and granular wettable powder thus obtained are diluted with water to a predetermined concentration to obtain a powder, as a solution, suspension, or emulsion. Or granules are used as is.

[0081] The amount of the active ingredient contained in the agricultural and horticultural fungicide of the present invention is not particularly limited, but is preferably 0.01 to 90% by weight, more preferably 0, based on the entire composition (formulation). .05-85% by weight.

[0082] The formulated fungicidal composition of the present invention is applied to a plant, seed, water surface or soil as it is or diluted with water or the like. The application amount varies depending on weather conditions, formulation, application timing, application method, application location, disease to be controlled, target crops, etc., but is usually 1-1, OOOg in terms of the amount of active ingredient compound per hectal, preferably 10 ~: LOOg.

[0083] When a wettable powder, emulsion, suspension, aqueous solvent, granular wettable powder or the like is diluted with water and applied, the applied concentration is 1 to: L000 ppm, preferably 10 to 250 ppm. In the case of powders, powders, etc., apply as is without dilution.

[0084] Needless to say, the compound of the present invention is sufficiently effective when used alone, but it should be used in combination with one or more of various fungicides, insecticides, acaricides or synergists. You can also. These fungicides, insecticides, acaricides, and synergists can be contained in the agricultural and horticultural fungicides of the present invention, and are used in combination when applying the agricultural and horticultural fungicides of the present invention. It can also be done.

[0085] Representative examples of fungicides, insecticides, acaricides, and plant growth regulators that can be used by mixing with the compound of the present invention are shown below.

[0086] Disinfectant:

Quybutane, phorpet, thiuram, ziram, dineb, mannebu, mancozeb, propineb, polycarbamate, chlorothinine, quintozene, captaphor, diplodione, prosiminone, fluorimide, meprol, flutral, pencyclon, oxycarboxy , Fosetyl aluminum, propamocurve, triadimethone, triadimenol, propiconazonole, diclobutrazoneore, bitenoretanonore, hexaconazonole, microbutaninole, flusilazole, etaconazole, flutrimazole, flutriafen, penconazonore, diniconasole , Cyproconazoles, Fenarimonore, Trifnore Misonore, Prok Mouth Raz, Imazalinole, Pephrazoate, Tridemonolev, Fenpropimonolev, Triforine, Butiobeto, Pyriphenox, Arazine, Polyoxin, Metalaxyl, Flaxilil, Flaxilil Isoprothiolane, probenazole, pyrrolnitrin, blasticidin s, kasugamycin, noridamycin, dihydrostreptate Tomycin, Benomyl, Carbendazim, Thiophanate Methyl, Himexazole, Basic Copper Chloride, Basic Copper Sulfate, Phentin Acetate, Hydroxyl Triphenyl Tin, Dietophene Calp, Quinomethionate, Vinapatalyl, Lecithin, Baking Soda, Dithianone , Zinocup, phenaminosulf, dichromedin, guazatine, dodine, IBP, edifenphos, mepa-pyrim, phenolemzone, trichlamide, metasulfocarb, fluazinam, etokinolac, dimethomorph, pyroxylone, technophthalam, fusalide, phenazine oxide, Thiabendazole, tricyclazole, vinclozolin, simoxal, cyclobuta- ral, guazatine, propamocarb hydrochloride, oxolinic acid, cyflufenamide, iminoctazine, taresoxime , Triazine, fenhexamide, cyazofamide, cyprozil, prothioconazole, fenbuconazole, trifloxystrobin, hexoxystrobin, hexaconazole, imibenconazole, tebuconazole, diphenoconazole, quinomethionate, Carpropamide.

Insecticides, acaricides:

Organophosphorus and carbamate insecticides:

Fenthion, fenitrothion, diazinon, chlorpyrifos, ESP, bamidthione, phenate, dimethoate, formothione, marathon, trichlorfone, thiomethone, phosmet, dichlorvos, acephete, EPBP, methyl parathion, oxidimethone methyl, ethion, salithione, thionopion, thionopion, thionopion Hosalon, methidathion, sulprofos, clonolephine phos, tetrachlorbin phos, dimethylvin phos, propaphos, isofenphos, ethinoretiomethone, profenophos, pyracrofos, monocrotophos, azinphosmethyl, aldicarb, mesomil, thiodicarp, carbofura , Carbosulfur, Benfuracarb, Fraciocarp, Provoxur, BPMC, MT MC, MIPC, Power Lubaryl, Pirimicurve, Ethiophene Calp, Phenoxycalp, Caltap, Thiocyclam, Bensultap, etc.

[0088] Pyrethroid insecticides:

Penoremethrin, cypermethrin, deltamethrin, fenvalerate, fenpronotrin, pyrethrin, allethrin, tetramethrin, resmethrin, dimesulin, propraslin, phenothrin, protorin, fulvalinate, cyfluthrin, sino-rotrin, flucitrinate, etofenprottus, cycloprotoline , Tralomethrin, shiranoleofene, acrinatrin, etc.

[0089] Benzylurea and other insecticides:

Difunolebenzuron, Chlorfluzuron, Hexaflumuron, Trifunolemuron, Funolefenoxuron, Funolecyclotusuron, Buprofezin, Pyriproxyfen, Metoprene, Benzopin, Difenthiuron, Imidacloprid, Fiprole, Nicotine sulfate , Rotenone, metaldehyde, acetamiprid, chlorfenavir, ditenbiram, thiacloprid, clothiazine, thiamethoxam, dinotefuran, indoxacarp, pymetrozine, spinosad, emamectin, pyridalyl, tebufenozide, chromafenodid, methoxyfenobid Oil, microbial pesticides such as BT and entomopathogenic viruses.

[0090] Nematicides:

Fuenamifos, Phostiazate, Kazusafos etc.

Acaricide:

Chlorbendilate, feso-sobromolate, dicophore, amitraz, BPPS, benzomate, hexithiazotas, phenbutatin oxide, polynactin, quinometinate, CPCBS, tetradiphone, avermectin, milbemectin, clofuentezin, cihexatine, pyridaben, fenpyroximate, Tebufenvirad, pyrimidifene, fenotiocarp, genoclor, fluatalipyrim, acequinosyl, bifenazate, etoxazole, spirodiclofen, fenazaquin and the like.

[0091] Plant growth regulator:

Gibberellins (eg gibberellin A3, gibberellin A4, gibberellin A7) IAA, NAA. Example Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

Example 1 Preparation of methyl N, mono (2 chloro-5- {4 [1 mono (2 fluorophenyl) cyclopropyl] thiazole-2-yl} phenol) hydrazinecarboxylate

(1) Manufacture of 1 1 [1 1 (2-fluorophenyl) cyclopropyl] ethanone

[0094] [Chemical 12]

[0095] 1- (2 Fluorophenol) propan-2-one 5. Og (32.9 mmol) was dissolved in 50 ml of N, N dimethylformamide. After adding 1.58 g (39.5 mmol) of 60% oily sodium hydride at 0 ° C., 7.4 g (39.4 mmol) of 1,2 dibromoethane was added and stirred at the same temperature for 1 hour. After warming to room temperature, the reaction mixture was further charged with 1.58 g (39.5 mmol) of 60% oily sodium hydride. After stirring at room temperature for 2 hours, the reaction mixture was cooled to 0 ° C., added with 1,2 dibromoethane (3.lg) (16.5 mmol), warmed to room temperature, and stirred for 1 hour. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated from the filtrate under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent: benzene ethyl acetate = 19: 1 (volume ratio)) to obtain the desired 1- [1- (2 fluorophenyl) cyclopropyl] ethanone. 2. 5g was obtained. Yield 43%

[0096] (2) Preparation of methyl N, 1 (2 chloro-5- {4 [1 (2 fluorophenol) cyclopropyl] thiazo 1 lou 2 -yl} phenol) hydrazinecarboxylate

[0097] [Chemical 13]

[0098] Bromine 0.30 g (l. 9 mmol) was dissolved in a solution of 1- [1— (2 fluorophenyl) cyclopropyl] ethanone 0.32 g (l. 8 mmol) obtained in the above in 5 ml of benzene. Of benzene (3 ml) was added and aged at 40 ° C for 2 hours. By concentrating the reaction solution, a crude product of 2-promo 1 [1 (2-fluorophenyl) cyclopropyl] ethanone was obtained. In a solution of the obtained 2-bromo 1- [1- (2-fluorophenyl) cyclopropyl] ethanone crude product dissolved in 10 ml of methanol, N, 1 (2 chloro-5 thiocarbamoylphenol) hydrazine was added. 0.33 g (l. 4 mmol) of methyl carboxylate was added and refluxed for 1 hour. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off from the filtrate under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent: benzene ethyl acetate = 19: 1 (volume ratio)) to obtain the target N,-(2 black mouth 1-5- {4— [1— 0.18 g of methyl (2-fluorophenyl) cyclopropyl] thiazole 2-yl} phenol) hydrazine carbonate was obtained. Yield 34%

The compounds produced in the same manner as in Example 1 are shown in Tables 1, 2 and 3.

[0099] [Table 1] Table 1

Acho f¾ 0

2] 2

3] 

(HS 'ΡΡ) Ζε Ί' (ΗΖ 'ΡΡ) 28 Ί' (Η ε ^<s ) zz ε ′ (ΗΙ Ά) ε 99 '(HI' S) -g '(HI ^ q) o' L '(HZ' ^) Z 'LL' L

• (^ dcj g 'S ^{, S} 10aO) H NH _x O) (^ 9)-^ i¾J ^ [WHO]

(HS 'PP) OS Ί' (HS 'ΡΡ) 9 Ζ Ί' (Η ε ^<s ) 8z ε '(HI' jq) s 9 '(HI' S) O 9 '(HI ^ q) 9 '(HZ' ^) Ο Ί-9 'L

• (^ dcj g 'S 丄' ^ε ΐθα) ΉΙ N—H _T ) (0) Each 粱呦 I * [SOTO]

·) Stop ^ — ^ /

[20 TO]

HZ

Z6LLU / 900Zdr / 13d C6.6Z0 / .00Z OAV [0105] * 3 ¹ H-NMR (CDC1, TMS, δ ppm) of Compound No. (59);

Three

7. 6- 7. 0 (m, 7H), 6. 7 (br, 1H), 6. 41 (s, 1H), 6.3 (br, 1H), 3. 77 (s, 3 H), 2.36 (s, 3H), 1.64 (dd, 2H), 1.29 (dd, 2H)

[0106] Next, some examples of the bactericidal insecticide composition of the present invention are shown. Various additives and their addition ratios can be changed in a wide range, not limited to the following examples. The part in a formulation example shows a weight part.

(Formulation Example 1) Wetting agent

40 parts of the present compound

Clay 48 咅

Dioctylsulfosuccinate sodium salt 4 parts

Lignosulfonic acid sodium salt 8 parts

The above was mixed uniformly and finely pulverized to obtain a wettable powder with 40% active ingredient.

(Formulation Example 2) Emulsion

Compound of the present invention 10 parts

Sonorebessa 200 53 咅

26 parts of cyclohexanone

1 part calcium dodecylbenzenesulfonate

10 parts of polyoxyethylene alkylaryl ether

The above was mixed and dissolved to obtain an emulsion with 10% active ingredient.

[Formulation Example 3] Powder

Compound of the present invention 10 parts

Clay 90 咅

The above was mixed uniformly and finely pulverized to obtain a powder with 10% active ingredient.

[0110] (Formulation Example 4) Granules

Compound of the present invention 5 parts

Clay 73

20 parts of bentonite

Dioctylsulfosuccinate sodium salt 1 part Potassium phosphate 1 part

The above was pulverized and mixed well, water was added and kneaded well, and then granulated and dried to obtain granules containing 5% active ingredient.

[0111] (Formulation Example 5) Suspension

Compound of the present invention 10 parts

4 parts of polyoxyethylene alkylaryl ether

Polycarboxylic acid sodium salt 2 parts

Glycerin 10 parts

Xanthan gum 0.2 parts

Wed 73.8

The above were mixed and wet-pulverized until the particle size became 3 microns or less to obtain a suspension with 10% active ingredient.

[0112] (Formulation Example 6) Granule wettable powder

40 parts of the present compound

Clay 36 咅

Salty potassium 10 parts

Alkylbenzenesulfonic acid sodium salt 1 part

Lignosulfonic acid sodium salt 8 parts

Of alkylbenzenesulfonic acid sodium salt

Formaldehyde condensate 5 parts

After mixing the above uniformly and finely grinding, an appropriate amount of water was added and kneaded into a clay. The clay-like product was granulated and dried to obtain a granule wettable powder containing 40% active ingredient.

[0113] Next, Test Examples show that the compounds of the present invention are useful as active ingredients of various plant disease control agents and insecticides. In the following, the compound numbers correspond to the compound numbers in Tables 1 and 2.

[0114] (Test Example 1) Apple scab control test

An apple seedling (cultivar “Kokumitsu”, 3-4 leaf stage) cultivated in an unglazed pot was sprayed with an emulsion of the compound of the present invention at a concentration of lOOppm of active ingredient. Apple scab after natural drying at room temperature Inoculated with conidia of fungi (Venturia inaequalis), the light and darkness were repeated every 12 hours and kept in a room at 20 ° C and high humidity for 2 weeks. As a result of comparing the appearance of lesions on the leaves with no treatment and obtaining the control effect, the compound number: 13, 40, 41, 44, 54, 55, 56, 58, 59 Showed an excellent control value of 75% or more.

[0115] (Test Example 2) Wheat powdery mildew prevention test

A wet seedling of the compound of the present invention was sprayed at a concentration of lOOppm on wheat seedlings (variety “Chihoku”, 1.0-1.2 leaf stage) cultivated in an unglazed pot. After the leaves were air-dried, conidia of wheat powdery mildew (Erysiphe graminis f. Sp. Tritici) were shaken off and inoculated, and kept in a 22-25 ° C warm room for 7 days. The lesion appearance on the leaves was compared with no treatment, and the control effect was obtained. As a result, the compound control number of 13, 40, 41, 44, 54, 55, 56, 58, 59 showed excellent control value of 75% or more.

[0116] (Test Example 3) Tomato plague control trial

Tomato seedlings grown in an unglazed pot (variety “Regina”, 4-5 leaf stage) were sprayed with an emulsion of the compound of the present invention at a concentration of lOOppm of active ingredient. After spraying, it is air-dried at room temperature, sprayed with a zoospore suspension of Phytophthora infestans, and kept in a high humidity constant temperature chamber (20 ° C) that repeats light and dark every 12 hours for 4 days . We compared the appearance of lesions on the leaves with no treatment, and determined the control effect. As a result, the compound Nos. 13, 40, 41, 44, 54, 55, 56, 58 and 59 showed an excellent control value of 75% or more.

[0117] (Test Example 4) Wheat red rust control test Wheat seedlings grown in an unglazed pot (variety “Noribayashi No. 61”, 1.0 to 1.2 leaf stage) were mixed with lOOppm of the wettable powder of the compound of the present invention. Scattered by concentration. After the leaves were air-dried, the summer spores of wheat rust (Puccinia recondita) were shaken / inoculated and kept in a 22-25 ° C greenhouse for 10 days. The lesion appearance on the leaves was compared with no treatment to determine the control effect. As a result, the compound Nos. 13, 40, 41, 44, 54, 55, 56, 58 and 59 showed an excellent control value of 75% or more.

Industrial applicability

[0118] According to the present invention, a novel aryl derivative or a salt thereof, which has an excellent controlling effect for controlling diseases of useful plants, and one or more of these as an active ingredient An agricultural and horticultural fungicide is provided.

Claims

The scope of the claims

Formula (1)

[Wherein, R ¹ represents a C alkyl group or a C alkoxy group.

1-6 1-6

R ² is a halogen atom, C alkyl group, C alkoxy group, C hydroxyalkyl

1-6 1-6 1-6

Group, C alkyloxy C alkyl group, or C alkylcarboxoxy C

1-6 1-6 1-6 1 represents an alkyl group.

-6

R ³ is a halogen atom, C alkyl group, C alkoxy group, C hydroxyalkyl

1-6 1-6 1-6

Group, C alkyloxy C alkyl group, or C alkylcarboxoxy

1-6 1-6 1-6

C represents an alkyl group.

1-6

G represents an oxygen atom or a sulfur atom.

A represents any group represented by formula (2), (3), or (4).

[Chemical 2] R ⁴ R ⁵ R ^{6 (2)}

R ⁷ R ⁸

—— N— —— ⁽³⁾

— = —— (4)

(Wherein R ⁴ and R ⁷ are each independently a hydrogen atom, a C alkyl group, a C alkyl group,

1-6 represents a 1-6 rucarbonyl group or a C haloalkylcarbonyl group.

1 -6

Represents an alkyl group.

k represents an integer of 1 to 4. When k is 2 or more, the groups represented by the formula: —C (R ⁴ ) (R ⁶ ) — may be the same or different. )

Q ¹ represents any group represented by the formula (5), (6), (7), (8) or (9).

[Chemical 3]

(In the formula, R ⁹ represents a hydrogen atom, a halogen atom, a C alkyl group, or a C alkyl

1 -6 1 -6

Represents a bonyl group. E represents an oxygen atom or a sulfur atom. g represents an integer of 0 to 3. )

Q ² represents a phenol group or an aromatic heterocyclic ring.

R ^1Q represents any substituent that is chemically acceptable.

1 represents an integer from 0 to 4. When 1 is 2 or more, R ^1Q may be the same or different.

]

Or a salt thereof.

An agricultural and horticultural fungicide containing, as an active ingredient, one or more of the aryl heterocyclic derivatives represented by the formula (1) or salts thereof.