JPS61165308A - Fungicidal composition for agricultural and horticultural purposes - Google Patents

Abstract

PURPOSE:The titled composition that contains, as active ingredients, a novel aniline derivative and a benzimidazole fungicide, thus developing excellent pest-combating effect in lower concentration than that required, when it is used separately and preventing infestation in fields which have been infested with resistant microorganisms. CONSTITUTION:The objective composition contains, as active ingredients, a novel aniline derivative of the formula (X, Y are lower alkylene, lower alkoxy- lower alkylene; k, l, m and n are 0 or 1; R<1> is nitro, 2-nitrovinyl, amino, isothiocyanato, X is H, OH, lower alkyl, lower alkenyl, A is O, S; B is lower alkyl, lower alkenyl, lower cycloalkyl, phenyl) and at least one selected from benzimidazole fungicides, thiofanate fungicides or cyclic imide fungicides. The composition can be used to combat a variety of causative microorganisms such as cucumber powdery mildew and tomato gray mold.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides agricultural products containing as active ingredients one or more new aniline derivatives and one or more benzimidazo-V directicides, thiophanate fungicides, or cyclic imide fungicides. The present invention relates to a horticultural fungicidal composition.

Since systemic fungicides began to be used for crop disease control, the problem of drug-resistant bacteria has become critical. In fields where drug-resistant bacteria have spread, the drug cannot be expected to have sufficient efficacy. Such drugs include, for example, Penomi V [Methi A/1-(Buty V carbamoy/L/)benzimidazo-N-2-yl-bamate], Fubelidazo A/C2-(2-Furi A/)benzimidazo -v〕
, thiabendasi v [2-thiazol-4-iV benzimidazo-v], force V bendazim [methiV benzimidazo-A/-2-i [carbamate]], thiophanate methyl rv [dimethi IV 4 , 4-0-7 22ren
bis(8-cheoallophanate)], thiophanate [dithyl 4
．． benzimidazole-thiophanate fungicides such as 4-o-7 dinilene bis(8-thioallophanate)], and procymidone CN-(a',5'-diccxa
yx ditv')-1,2-dimethylcyclopropane-1
, 2-dicarboximide], iprodione (8-(8
',5'-dichlorophenyl)-N-4)/7'robi/l/-2゜4-dioxoimidazolidine-1-carboxamide], vinclozolin (8-(8',5'-diclophenyl)-5 Cyclic imide-based sterilization such as -methyv-5-vinyv-1゜8-oxazolidine-2,4-dione], dicrosilinate [methyN8-(8',5'-diclophenyloxazolidine-5-carboxylate]) Examples include agents.

In view of this situation, the present inventors conducted various studies in order to develop a compound that is effective against the aforementioned drug-resistant bacteria. , a lower alkylene group is a lower alkoxy lower 11V kylene group.

k, l*m and n are the same or different, 0 or 1
represents.

R1 is a nitro group, a 2-nitroviny V group, an amino group, an isothiocyanato group, a lower alkali V amino group, or the general formula =NH-8-R2, -0-5-R1! , -S-A
'-Rt.

A group represented by -5O2-NH-R2 or -5-R2↓ (O).

(Here, A' and Ni' are the same and -te are different and represent an oxygen atom or a sulfur atom, and R2 and R'
meanings are the same or different, lower alkyl group, lower alkenyl group, lower alkyl group, lower m halo rvJfvj
l, or a lower alkoxyalkyl group, p is 0
, 1 thought represents 2. ).

2 represents a hydrogen atom, a hydroxyl group, a lower alkyl group, a lower alkenyl group, a lower alkenyl group, a lower alkoxy group, a group represented by the general formula -〇-R, or -SR4 ( Here, R8 represents a lower aleki V group, a lower cycloa V group, and a phenyl μ group;
4 is a lower alkyl group, a phenyl group or a lower alkyl group
V represents a bondyl group. ).

A represents an oxygen atom or a sulfur atom.

B represents a lower alkyl group, a lower alkenyl group, a lower cycloa group, a phenyl group or a substituent represented by the general formula -W-R5 (where W is an oxygen atom or a sulfur atom) and R6 represents a lower alkyl group, a lower alkenyl group, a lower akini V group, a lower haloalkeni V group, a lower herooalkynyl V group, or a lower cycloalkyl group, or a phenyl group optionally substituted with a halogen atom. 9 represents an alkyl group substituted with at least one atom or group selected from a halogen atom, a cyano group, a phenylene group, a lower cycloalkyl group, or a lower AV-koxy group). ] We have discovered an aniline derivative represented by the following.

However, in actual fields where pathogens are prevalent, drug-resistant bacteria and wild bacteria that are sensitive to benzimidazole-thiophanate fungicides or cyclic imide fungicides often coexist.

Therefore, as a result of further various studies, the general formula [■
By using a mixture of one or more of the aniline derivatives shown in ] and one or more of the benzimidazole thiophanate-based FF fungicides or cyclic imide-based fungicides,
It became clear that the disease control effect was higher than when they were used alone, and even at low concentrations.

Therefore, the composition of the present invention has high practical value as a fungicide that exhibits excellent pest control effects.

Furthermore, the composition of the present invention can prevent the spread of drug-resistant bacteria by continuously spraying benzimidazole-thiophanate fungicides or cyclic imide fungicides in fields where drug-resistant bacteria have not appeared. Its appearance can be prevented.

Since the composition of the present invention has excellent bactericidal activity against a wide range of types of filamentous MVc, it can be used for controlling various pathogens occurring in agriculture and horticulture.

Such pathogens include, for example, powdery mildew of apples (Podosphaera 1eoucotric).
ha).

Venturia 1naequalis
, Sclerotinia mali
, oyster anthracnose fungus (Gloeosporfum kak)
i), Sclerotinia ci
nerea), C1ados-poriu
M carpophilum), Botrytis cinerea, Elsinoeampeline, Gl.
Cercospora beticola), Cercospora beticola
), Cercospora a
rachidi-co]a), Cerco
spora personata), barley powder and disease fungus (Erysiphe graminisf, s
P. hordei), Ai, spot fungus (Cerc.
os-porella herpotrichoid
s), Fusarium n1va
le), wheat powdery mildew fungus (Erysiphe
graminis f, spa tritici)
, cucumber powdery mildew fungus (Sphaerothec)
a fuligi-nea), Vine blight fungus (Myc
osphaerella melonis), Botrytis cinerea, Cladosporium cucumerinee
m), tomato mold fungus (Cladosporiu
M fulvum), botrytis fungus (Botryti
s cineraa), powdery mildew fungus (Sp
haerotheca humuli), Botrytis cinerea on hops, and Erysiphe cichora on tobacco.
cearum), Diplocarp
on rosae), tangerine scab fungus (Elsin
oe fawcetti), Blue mold fungus (Penic
illium italicum), green mold fungus (Pe
nicillium digitatum).

Furthermore, the composition of the present invention is highly safe for humans, livestock, and fish, and can be used without actually causing any harm to commercially useful crops.

Next, a reference production example of the aniline derivative represented by the general formula CI''J of the present invention will be shown.

Reference production example 6.8-diamino-1,8-benzodioxa: /8.8
21. Methyl chloroformate 8.78 to a mixture of N,N-die 4-U): /6.00F and 50m of dioxane
1 was added dropwise over 6 minutes under water cooling. After the reaction solution was left at room temperature for 12 hours, it was poured into ice water and extracted with ethyl acetate M. After washing the organic layer with water, it was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
It was purified by silica gel column chromatography using a fi mixed solvent of diamine and ethyl acetate to obtain 6,8-bis(methoxycarboniV-amino)-t,a-benzodioxane [Compound No. (44) 14.94F]. Ta.

Yield 87.5% m, p, 156.5-157.5°C Similarly, 6-ituderoboxica MbonyMamino-8-methoxycaMbonyV amino-1,8-penzodioxane [Compound No. (42) ] m, p, 159-160.5°C, 6-nitoxycarbony M amino-8-methoxy force V bonyl raremino-1,3-benzodioxane [Compound No. (48)) m, p, 149-150°C was obtained .

The aniline derivatives represented by the general formula [I] thus obtained are illustrated in Table 1.

Examples of benzimidazole fungicides include methyl 1-(butylcarbamoyl)benzimidazole-2-yl-bamate (hereinafter referred to as compound A) represented by the formula %, 2-( represented by the formula 4-thiazolyl)benzimidazole (hereinafter referred to as compound B), methylbenzimidazole-2-ylbamate (hereinafter referred to as compound C) represented by the formula, 2-(2-furyl) represented by the formula Examples include benzimidazole (hereinafter referred to as compound),
Examples of thiophanate fungicides include 1,2-bis(8-methoxycarbonyl-2-thioureido)benzene (hereinafter referred to as compound E) represented by the formula, 1,2-bis(8- ethoxycarbonyl-2
-Thioureido)benzene (hereinafter referred to as compound F)
, 2-(0,S-dimethylphosphorylamino) represented by the formula
-1-(3'-methoxycarbonyl-2'-thioureido)benzene (hereinafter referred to as compound G), 2-(0,0-dimethylthiophosphorylamino)-t-(a'-methoxy carbonyl-2'-thioureido)benzene (hereinafter referred to as compound H), and examples of mamaru cyclic imide fungicides include N-(8',5'-dichlorophenyl)-1 shown by the formula
, 2-dimethylcyclopropane-1,2-carboximide (hereinafter referred to as compound engineering), 8-(8',6'-dichlorophenyl)-1 represented by the formula % formula %
-isopropylcarbamoylimidazolidine-2,4-
Dione is hereinafter referred to as compound J. ), 8-(8',5'-dichlorophenyl)-5 represented by the formula
-Methyl-5-vinyloxazolidine-2゜4-dione (hereinafter referred to as compound), ethyl (R
3) -8-(8',5'-dichlorophenyl)-5-methyl-2,4-dioxoxazolidine-5-carboxylate (hereinafter referred to as compound).

Next, formulation examples of the composition of the present invention will be shown.

Formulation Example 1 Powder 1 part of Compound (44), 1 part of Compound I, 88 parts of clay and 10 parts of talc are thoroughly ground and mixed to obtain a powder with a base ingredient content of 2%. Right formulation example 2 Wettable powder compound (44) 20 parts, compound 1 10 parts, diatom ±45
By thoroughly grinding and mixing 20 parts of white carbon, 8 parts of a wetting agent (sodium lauryl sulfate), and 2 parts of a dispersing agent (calcium lignin sulfonate), a wettable powder having a base ingredient content of 80% is obtained.

Formulation Example 8 Wettable powder Compound (44) 10 parts, Compound A 40 parts, Diatom ±4
5 parts, 2.5 parts of wetting agent (calcium alkylbenzenesulfonate), and 2.5 parts of dispersing agent (calcium lignin sulfonate) are thoroughly ground and mixed to obtain a base ingredient content of 50%.
to obtain a hydrating agent.

Formulation Example 4 Emulsion 5 parts of Compound (44), 5 parts of Compound F, 80 parts of cyclohexanone, and 10 parts of an emulsifier (polyoxyethylene alkyl allyl ether) are mixed to obtain an emulsion with a base agent content of 10%.

In the above formulations, the active compound is generally present in amounts ranging from L O to
95.0%, preferably 2.0-80.0%. In addition, the composition of the present invention usually has a concentration of 10 to 100 N per 10 ares.
The application amount is appropriate.

The concentration used is preferably in the range of 0.005 to 0.6%, but the amount and concentration used vary depending on the dosage form, application time, method, location, target disease, target crop, etc., so do not limit yourself to the above range. There is no problem in increasing or decreasing the amount without any problem.

Furthermore, it can be used in combination with other fungicides, herbicides, plant growth regulators and insecticides.

For example, Sn-butylS-p-tert-butylbenzyltheocarbonimide), 0.0-dimethyl 0-
(2,6-dichloro-4-methylphenyl)phosphorothioate, N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide, polyoxin, streptomycin, zinc ethylene bisdithiocarbamate, tetrachloroinphthalonitrile, 8 -hydroxyquinoline, N″-dichlorofluoromethylthio-N,
N-dimethyl-N-phenylsulfamide, 1-(4-
chlorophenoxy)-8,3-dimethyl-1-(1,2
, 4-triazol-1-yl)-2-butanone, methyl N-(2,6-dimethylphenyl)-N-methoxyacetyl-2-methylglycinate, aluminum ethyl phosphite, etc., 2,4- Phenoxy herbicides such as dichlorophenoxyacetic acid, diphenyl ether herbicides such as 2,4-dichlorophenyl 4'-nitrophenyl ether, 2-chloro-4,6-bisethylamino-1,8,5-triazine, etc. Triazine herbicide,
8-(:(,4-dichlorophenyl)-1゜Urea-based herbicides such as 1-dimethylurea, isopropyl N-(11-
Carbamate herbicides such as chlorophenyl) carbamate, thiol carbamate herbicides such as 5-(4-chlorobenzyl)N,N-diethylthiol carbamate,
Acid anilide herbicides such as 8゜4-dichloropropionanilide, uracil herbicides such as 5-bromo-85ec-butyl-6-methyluracil, 1゜1'-dimethyl-4
, 4'-bipyridinium chloride and other pyridinium salt herbicides, N-(phosphonomethyl)glycine, 0-ethyl 0-(2-nitro-5-methyl 4-phenyl) N-se
c-Butyl phosphoroamide thioate is 5-(2-
Phosphorus herbicides such as methyl-1-piperidylcarbonylmethyl)0゜O-di-n-propyl ditheophosphate,
α,α,α-trifluoro2゜6-sinitroN,N
-Toluidine herbicides such as dipropyl-p-toluidine, organophosphorus insecticides such as 0,0-dimethyl 0-(4-nitro-8-methylphenyl)phosphorothioate, α-
Cyano-3-phenoxybenzyl 2-(4-chlorophenyl)isovalerate, 8-phenoxybenzyl 2.2
-Pyrethroids such as dimethyl-8-(2,2-dichlorovinyl)cyclopropanecarboxylate, α-cyano-8-phenoxybenzyl 2,2-dimethyl-8-(2,2-dibromovinyl)cyclopropanecarboxylate, etc. It can be used in combination with insecticides, and neither of them will reduce the control effect of each agent alone, and a synergistic effect is also expected by mixing.

Next, test examples will be given to further clarify the usefulness of the composition of the present invention as an agricultural and horticultural fungicide.

Test Example 1 Cucumber Powdery Mildew Control Effect A 90-volume plastic pot was filled with sandy loam, and cucumbers (product 8
1: Sagami Half Day) was sown. This was cultivated at room temperature for 8 days, and the cotyledons developed to obtain nine cucumber seedlings. An emulsion of an aniline derivative with the following compound number prepared according to Formulation Example 4, a water-diluted solution of a hydrating powder of compounds A to H, and a mixture thereof are sprayed on these seedlings until a sufficient amount of droplets adhere to the leaf surface. did. After air-drying the chemical solution, the seedlings were infected with cucumber powdery mildew fungus (Sph).
A conidial suspension obtained by mixing drug-resistant and susceptible bacteria of A. ae-rotheca fuliginea was sprayed onto the cells. After cultivating the plants in a greenhouse for 10 days to develop the disease, the state of disease development was observed.

The disease severity was calculated using the following method.

That is, depending on the appearance of lesions on the investigated leaves, 0% 0.5.1
．． The disease was classified into an index of 2.4, and the disease severity was calculated using the following formula.

(Number of disease symptoms) (State of disease development) No bacterial flora or lesions were observed on O96100 leaves.

0.5゜0600 Bacterial flora or lesions are observed on less than 5% of the leaf area.

1. Bacterial flora or lesions are observed on the leaf surface in less than 20% of the leaf area.

2. Bacterial flora or lesions are observed on the leaf surface in less than 60% of the leaf area.

4. Lesions with bacterial flora are observed on the leaf surface over 50% of the leaf area.

Next, the control value was calculated using the following formula.

As a result, as shown in Table 8, the aniline derivative and compound A
When either of -H was mixed and sprayed, a superior control effect was observed compared to when they were sprayed alone.

Table 211 Test Example 2 Tomato gray mold control effect A 90-volume plastic pot was filled with sandy loam, and tomatoes (variety Nifukuju No. 2) were sown. This was cultivated in a greenhouse for 4 weeks to obtain tomato seedlings at the 4-leaf stage. To this was prepared an emulsion of an aniline derivative with the following compound number, compound 1-L, prepared according to Formulation Example 4.
10 Wt of a water-cooled dilution of the hydrating powder and the mixture thereof was sprayed on the foliage per pot. After air-drying the chemical solution, Botrytis cinerea
A nonadian spore solution obtained by mixing drug-resistant and susceptible bacteria was inoculated by spraying. After this was kept in a humid greenhouse at 20°C for 5 days, the disease state was observed. The disease onset investigation method and control value calculation were performed in the same manner as in Test Example 1.

As a result, as shown in Table A, aniline derivatives and compounds I~
Table 4 shows that when sprayed in combination with either of L, a superior control effect was obtained compared to when they were sprayed alone.

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X and Y are the same or different and represent a lower alkylene group or a lower alkoxy lower alkylene group. k, l, m and n are the same or different, 0 or 1
represents. R_1 is a nitro group, 2-nitrovinyl group, amino group, isothiocyanato group, lower alkylamino group, or general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, -NH-S-R_2, -O-S-R_2, -S-A'-
R_2, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -SO_
2-A'-R_2 -SO_2-NH-R_2 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, A' and A'' are the same or different, and represent an oxygen atom or a sulfur atom. (wherein, R_2 and R'_2 are the same or different and represent a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower haloalkyl group, or a lower alkoxyalkyl group, and p represents 0, 1 or 2). Represents a hydrogen atom, a hydroxyl group, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower alkoxycarbonylalkyl group, or a group represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ or -SR_4 (where R_3 is (Represents a lower alkyl group, lower cycloalkyl group or phenyl group, R_4 represents a lower alkyl group, phenyl group or lower alkoxycarbonyl group.) A represents an oxygen atom or a sulfur atom. B represents a lower alkyl group, lower alkenyl group, lower cycloalkyl group, phenyl group or general formula -W-
Represents a substituent represented by R_5 (where W represents an oxygen atom or a sulfur atom, R_5 is a lower alkyl group,
Represents a lower alkenyl group, lower alkynyl group, lower haloalkenyl group, lower haloalkynyl group, or lower cycloalkyl group, or represents a phenyl group optionally substituted with a halogen atom, or represents a halogen atom, a cyano group, or a phenyl group. represents an alkyl group substituted with at least one atom or group of a group, a lower cycloalkyl group, or a lower alkoxyl group. ). ] An agricultural and horticultural fungicidal composition containing as active ingredients one or more of the aniline derivatives shown below and one or more of a benzimidazole fungicide, a thiophanate fungicide, or a cyclic imide fungicide. .