JPS59210064A - Aniline derivative, its preparation and agricultural and horticultural fungicide containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [X is nitro, amino, thioisocyanato, group of formula II (A' is O or S; R<2> is lower alkyl, lower alkenyl, etc.), etc.; Y is lower alkyl, lower alkoxy, H, etc.; A is O or S; B is lower alkyl, lower alkenyl, lower cycloalkyl, etc.]. EXAMPLE:Isopropyl N-(3-chloro-4-ethoxy-5-methoxycarbonylaminophenyl)-carbamate. USE:An agricultural and horticultural fungicide effective to powdery mildew, scab, etc. of apple. It exhibits strong fungicidal effect against fungi resistant to benzimidazole thiophanate fungicides. PROCESS:The compound of formulaIVcan be prepared by reacting the compound of formula III (R1 is lower alkyl, lower alkenyl, etc.) with the compound of formula IV (Z is halogen).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula [I] -A'-R2 represents a group represented by (hereinafter referred to as 11゜), A' and A'' are the same or different and represent an oxygen atom or a sulfur atom, and R2 is a lower alkyl group, a lower alkenyl group, a lower alkynyl group. , a lower haloalkyl group or a lower alkoxyalkyl group).Y represents a lower alkyl group, a lower alkoxyl group, a lower alkoxycarbonyl group, a hydrogen atom, a halokene atom or an acyl group.R1 represents a lower alkyl group, a lower alkenyl group,
Represents a lower alkynyl group, lower haloalkyl group, lower alkoxyalkyl group, lower cycloalkylalkyl group or lower cyanoalkyl group. A represents an oxygen atom or a sulfur atom. B is a lower alkyl group, lower 7 JL/
)) Represents a nyl group, a lower cycloalkyl group, a phenyl group, or a substituent represented by the general formula -W-Ra (where W represents a sulfur atom, and is assumed to be a lower alkyl group, a lower Represents an 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 a halogen atom or a cyano group. , phenyl group, lower cycloalkyl group, lower alkoxyl group, lower alkenyloxy group,
(Ill haloalkoxy group, phenoxy group represents an aral group substituted with at least one atom or group of an aralkyloxy group). The present invention relates to an aniline derivative represented by (hereinafter referred to as the compound of the present invention), a method for producing the same, and an agricultural and horticultural fungicide containing the same as an active ingredient.

The inventors have discovered that benomyl [methyl 1-(butylcarbamoyl)benzimidazole-2-yl-bamate]
, fubelidazole [2-(2-furyl)benzimidazole], thiabendazole [2-(4-thiazolyl)benzimidazole], carpendazim [methyl benzimidazole-2-ylbamate], thiophanate methyl [1,2-bis( 3-methoxycarbonyl-2
-thiourido)benzene], thiophyi, -)-[J
, , 2-bis(3-ethoxycarbonyl-2-thioureido)benzene], and procymidone [N-(8',
5'-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide], iprodione [3-(3', 5'-dichlorophenyl)-1-
isopropyl rubbermoyl εdacilidine-2,4-dione], vinclozolin [8-(3', 5'-dichlorophenyl)-5-methyl-5-vinyl-oxazolidine-2,4-dione], ethyl (S) - 8-(
3', 5'-dichlorophenyl)-5-methyl-
Shows a selective bactericidal effect against plant pathogenic bacteria and other filamentous fungi (hereinafter referred to as drug-resistant bacteria) that are resistant to cyclic imide fungicides such as 2,4-dioxoxazolidine-5-carboxylate. As a result of our earnest efforts to invent a disinfectant, we discovered that the aniline derivative represented by the general formula CD exhibits such an effect. That is, as is clear from the test examples described below, the compounds of the present invention are effective against diseases caused by wild bacteria that are susceptible to benzimidazole-thiophanate fungicides or cyclic imide fungicides (hereinafter referred to as drug-susceptible bacteria). Although it does not show any control effect, it shows an excellent control effect against diseases caused by drug-resistant bacteria.
The bactericidal activity of the compounds of the present invention against drug-resistant bacteria was extremely selective.

As mentioned above, the compound of the present invention exhibits a strong bactericidal effect selectively against bacteria that are resistant to benzimidazole/thiophanate fungicides. It can be used to control resistant bacteria. Examples of such bacteria include, for example, powdery mildew of apples (Podosphaera
Ieou-cotricha), Ven
turia 1naequalis), pear scab fungus (Venturia nashicola), monilia fungus (5clerosinia mali),
Oyster anthracnose fungus (Gloeosporium kak)
i), 8clerotinia c
inerea), Iad-ospori
um carpophilum), grape gray mold fungus (Botrytis ctnerea),
El-sinoe ampelina
), late rot fungus (Gjomerella cingula
ta), Cercos-por
a beticola), peanut blight fungus (
Uercospora arachidicola
), Cercospora person
ata), barley powdery mildew fungus (Erysip
He graniinis f, sp, hor
dej), eye spot fungus (0ercospore)
lla herpot-richoides),
Fusarium n1vale, wheat powdery mildew (Erysiphe gran)
inis.

f, sp, tritici), cucumber powdery mildew fungus (5phaerot, hean fulig)
inea), Mycosphaerel
la melonis), gray mold fungus (Bot
'rytis cinerea), Aspergillus sclera (O
lados-porium cucumerinum
), tomato leaf mold fungus (C1adosporiur
n fulvum), gray mold fungus (Botryt
is cinerea), strawberry powdery mildew fungus (
5pbaerotlleca bumuli), hop gray mold fungus (Botrytis ciner)
ea ), tobacco powdery mildew (Erysiphe
cichoracearum), Diplocarpon rosae on roses, Elsinoe fawcetii on mandarin oranges
), Blue mold fungus (Penjcilljum jt
aljcum), green mold fungus (Penicilli)
um digitatum).

As a result of further studies, it was found that the compound of the present invention is effective against the rice blast fungus (Pyri-cularia), regardless of the presence or absence of drug resistance.
It was found to be effective in controlling insects such as P. oryzae).

Although all of the compounds of the present invention have practically sufficient bactericidal activity, compounds of the above general formula CD are preferred.
Examples include aniline derivatives in which the substituent Y represents a lower alkyl group, a lower alkoxyl group, a lower alkoxyalkyl group, a halogen atom, or an acyl group.

More preferably, in the general formula [1], the substituent X represents a group represented by the general formula -Nu-C-几'2 or 11°-NH-C-A'-B'2, where: +1°A and A have the same meanings as above, and R'2 represents a lower alkyl group. ), Y represents a lower alkyl group, a lower alkoxyl group, a halogen atom or an acyl group, and R
1 represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower haloalkyl group, a lower alkoxyalkyl group, or a lower cyanoalkyl group, and when B is represented by the general formula -W-R8, 几8 represents a lower alkyl group. Examples include aniline derivatives as shown below.

Next, a method for producing the compound of the present invention will be described.

The compound of the present invention can be produced, for example, by the following method.

Manufacturing method (a) General formula [11,1 [In the formula, X, Y and R1 have the same meanings as above.

] A compound represented by the general formula [m] Z -0-B []II]I In the formula, 2 represents a halogen atom. B represents the same meaning as above. ] A manufacturing method of reacting with the compound shown in

This reaction can be carried out using, for example, water or an organic electrolyte such as benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, chloroform, carbon tetrachloride, ethyl acetate, pyridine, dimethylbormamide, or the like.
It is usually carried out in a mixture of pyridine, triethylamine, H,N-diethylaniline, potassium hydroxide, etc., and if necessary, a phase transfer catalyst such as tetrabutylammonium bromide. It can be carried out with high yield. By cooling or heating (0 to 150'C) as necessary, the reaction can be completed within 10 hours and the desired product can be obtained in good yield.

In the above production method, the compound represented by the general formula [11] is represented by the general formula [■] [wherein, X, Y and R1 represent the same meanings as above.

It can be obtained by reducing the nitrobenzene derivative shown in . For example, a method can be used in which reduction is performed using sodium sulfide or dihydrium hydrogen sulfide in a mixture of water and a lower alcohol such as methanol or ethanol. The reaction is usually completed within 12 hours at a temperature range from 50°C to the solvent reflux temperature. Or acetic acid, hydrochloric acid,
This can be carried out by a method using iron powder, zinc powder, or soot powder in a mixture of an inorganic acid such as sulfuric acid and water. The reaction is usually carried out at 50°C to 100°C and is completed within 12 hours. Furthermore, a method of hydrogenation using a catalyst such as platinum dioxide or palladium-carbon in an organic solvent such as ethanol or ethyl acetate under normal pressure or increased pressure, usually at 0°C to 60°C, can be used. In addition, the general formula [■]
The nitrobenzene derivative represented by, for example, the general formula [V
] [In the formula, X and Y represent the same meanings as above. ] 21-lophenol derivative represented by the general formula % formula %
[:] [In the formula, R1 represents the same meaning as above, and D represents a halogen atom, mesyloxy group or tosyloxy group.

] It can be obtained by reacting with the compound shown below.

The condensation reaction between the compound represented by the general formula [v] and the compound represented by the general formula [■] may be performed even if HfN, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran 5. Sodium hydroxide, potassium carbonate, N,N-diethylaniline, pyridine, etc. as necessary in a smg of dimanxane, toluene, benzene, ether, etc., or in a two-layer reaction system of toluene or benzene and water. The reaction can be carried out without a catalyst or in the presence of a phase transfer catalyst such as tetra-n-butylammonium bromide using a deoxidizing agent, and is usually completed within 12 hours at a temperature of 0'C to 100C.

Further, the nitrophenol derivative represented by the general formula [V] is, for example, the general formula [■] [wherein Y represents the same meaning as above]. ] and the general formula % formula % C, where R') is a lower alkyl group, a lower alkenyl group,
A lower haloalkyl group, a lower alkoxyalkyl group, or a group represented by the general formula -A''-R2 is represented here,
A' and 2 have the same meanings as above.), A' and 2 have the same meanings as above.].

This reaction can be carried out in the same manner as the reaction between the compound represented by the general formula [■] and the compound represented by the general formula [11] described above. In addition, the amine phenol derivative represented by the general formula [■] is, for example, J, Chem, So
c,, 1945.668 (substituent Y is methyl group 'r
ff), J, Chem, Sue,.

1896, 1321 (when substituent Y represents a methoxy group) and JP-A-52-122827 (when substituent Y represents a hydrogen atom or a chlorine atom).

Production method (b) General formula [K] [In the formula, X, Y, A and 1 represent the same meanings as above.] A compound represented by the general formula [x] Ra -W -H[X] [ In the formula, R8 and W have the same meanings as above.] A manufacturing method of reacting a compound represented by:

This reaction can be carried out without solvent or with benzene, toluene,
In an organic solvent such as xylene, diethyl ether, tetrahydrofuran, dioxane, N,N-dimethylformamide, chloroform, carbon tetrachloride, etc., without a catalyst or with triethylamine, N,N-diethylaniline, 1,4-diazabicyclo[2,2, 21), can be carried out with t-furan as a catalyst, optionally cooling or heating (0-5
0°C), the reaction can be completed within 10 hours and the desired product can be obtained in good yield.

In the above production method, the compound represented by the general formula [11'] can be obtained by reacting the compound represented by the general formula [■] with phosgene or thiophosgene. This reaction is carried out in an organic solvent such as benzene, toluene, xylene, ethyl acetate, or a mixture thereof, and is completed within 10 hours with good yield by heating from 50°C to reflux temperature if necessary. You can get what you want.

general formula [D l, where X is the general formula -Nu-C-2
(Here, R2 and A' have the same meanings as above), the compound of the present invention can be prepared by manufacturing method (0).
It can be manufactured by

Production method (0) General formula [X[] [In the formula, Y, R1, A and B represent the same meanings as above. ] A compound represented by the general formula [X [ ] ]-G-1 2 [X "
] [In the formula, approximately 2. A' and 2 have the same meanings as above. ] A manufacturing method of reacting with a compound represented by.

This reaction can be carried out in the same manner as the condensation reaction between the compound represented by the general formula [I[] and the compound represented by the general formula [111] in production method (a).

Compound [X[] has the general formula [XU [wherein Y, R1, A and B represent the same meanings as above]. ] It is obtained by reducing the compound shown by the manufacturing method (
8) It can be obtained in the same manner as the reduction reaction of the nitrobenzene derivative represented by the general formula [11'l] in f.

In addition, a compound represented by the general formula [Kawa] may be, for example, a compound represented by the general formula [Kawa] [where Y, A and B represent the same meanings as above. ] It is obtained by reacting the phenol derivative represented by the above general formula [W] with the compound represented by the general formula [W], and is obtained by the manufacturing method (a
) is obtained in the same manner as the reaction between the nitrophenol represented by the general formula [V] and the compound represented by the general formula [■].

In the above production method, the phenol derivative represented by the general formula [XIV
and B have the same meanings as above. ] It can be obtained by nitration of the compound shown in
The reaction can be carried out in good yield by any of the methods commonly used for the nitration of aromatic rings. For example, acetic acid,
A phenol derivative represented by the general formula [1] in a solvent such as concentrated sulfuric acid is heated with nitric acid (d = 1.52 to 1.5%) under cooling.
88) By gradually adding 7, the desired product can be obtained in high yield in a reaction time of 0.5 to 3 hours.The compound represented by the general formula [penalty] 11
uI] [wherein, Y represents the same meaning as above. It is obtained by reacting the aminophenol derivative represented by
The compound represented by the general formula [■] in L) and the general formula [
It can be obtained in the same manner as the reaction with the compound represented by I[1].

In addition, the compound represented by the general formula [discrete] is the general formula [■]! [In the formula, Y represents the same meaning as above. It is obtained by reducing the nitrophenol derivative represented by the formula [M] in the production method (a) in the same manner as the reduction reaction of the nitrobenzene derivative represented by the general formula [M]. Compounds represented by the general formula [correct], for example J, Org-C-he
It can be synthesized by the method described in J. M., 27.218 (1962).

In the general formula [I], X is of the general formula 10-A'-R
2II.

(where 几2.A' and A'
has the same meaning as above), the compound of the present invention can be produced by the production method (d).

Manufacturing method (d) General formula [Hiro] [In the formula, Y, R1, A, A' and B represent the same meanings as above. ] A manufacturing method of reacting a compound represented by the following with a compound represented by the general formula [XX] and 2-A -H[XX] [wherein 2 and A'' have the same meanings as above].

This reaction can be carried out in the same manner as the reaction between the compound represented by the general formula EXE and the compound represented by the general formula [X] in production method (b). Note that the compound represented by the general formula [X[X] is obtained by reacting the compound represented by the general formula [M] with phosgene or thiophosgene, and is It can be obtained from the compound shown in the same manner as the method for producing the compound represented by the general formula [R3].

Manufacturing method (6) General formula [double] [In the formula, X, Y, A and B represent the same meanings as above. ] A production method of reacting a compound represented by the above with a compound represented by the general formula [■].

This reaction can be carried out in the same manner as the reaction between the nitrophenol derivative represented by the general formula [V] and the compound represented by the general formula [■] in production method (a). General formula [
The compound represented by the general formula [XX[I] [wherein, X and Y represent the same meanings as above]. ] Obtained by reacting the compound represented by the above general formula [111] and the compound represented by the general formula [I] and the general formula [■] in production method (a)
It can be obtained in the same manner as the reaction with the compound shown. In the above manufacturing method, the compound represented by the general formula [XXII':l is obtained, for example, by reducing the nitrophenol derivative represented by the general formula [CI], and the compound represented by the general formula [■] in the manufacturing method (a). It can be obtained in the same way as the reaction for reducing .

Next, a manufacturing example will be shown.

Production Example 1 [According to production method (a). ] In a mixed solution of methyl N-(2-ethoxy-3-chloro-5-aminophenyl)carbame) L89fIN, N-diethylaniline 0.851 and toluene 15-,
Isopropyl chloroformate was added dropwise under water cooling for 5 minutes. After leaving the reaction solution at room temperature for 12 hours,
It was poured into ice water and extracted with ethyl acetate. After washing the organic layer with water, it was dried over anhydrous magnesium sulfate, and the bath medium was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography using toluene and ethyl acetate.
Isopropyl N-C8-chloro-4-ethoxy-5-methoxycarbonylaminophenyl)carbamate [Compound No. (2) 11.73f was obtained. (Yield 92.0%
) m, p, 140-142°C Production Example 2 [According to production method (b). ] Methyl N-(2-ethoxy-3-chloro-5-aminophenyl)carbamate 2.671 was dissolved in ethyl acetate 20-2, and 10-10 was added to an ethyl acetate solution containing 10 y of phosgene.
It was added dropwise at 20°C. After heating and refluxing for 30 minutes, the solvent was distilled off under reduced pressure and methyl N-(2
-ethoxy-3-chloro-5-isocyanatophenyl)
I got a carbamate. Without purification, this was converted into triethylamine 1,Of and 3-buten-2-ol 0.
The mixture was added dropwise to 50 grams of toluene solution containing 79f at room temperature.

After being left at room temperature for 12 hours, it was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography using a mixed solvent of toluene and ethyl acetate to obtain 1-methyl-2-propenyl N
-(3-chloro-4-ethoxy-5-methoxycarbonylaminophenyl)carbamate [Compound No. (8)
]8.579 was obtained. (Yield 95.6%) ny, o 1.5883 Production Example 3 [According to production method (e). ] Isopropyl N-(3-chloro-4-ethoxy-5-
To a mixed solution of 1.55 f of aminophenyl carbamate, 0.85 l of N,N-diethylaniline, and 15 g of toluene, 0.459 g of acetyl chloride was added dropwise over 5 minutes while cooling with water. After the reaction solution was left at room temperature for 12 hours, it was poured into ice water and extracted with ethyl acetate.

After washing the organic layer with water, drying with anhydrous magnesium sulfate,
The solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography using a mixed solvent of toluene and ethyl acetate to obtain isopropyl N-(8-chloro-4-ethoxy-5-acetylaminophenyl)carbamate [Compound No. (1):] 1.55 f was obtained. (Yield 86.5%) m, P, 178-174°C Production Example 4 [According to production method (d)] ] Isopropyl N-(3-chloro-4-ethoxy-5-
2.97f of aminophenyl) carbamate was dissolved in 20-ethyl acetate and added dropwise to an ethyl acetate solution containing 10y of phosgene at 10-20°C. After gradually heating and refluxing for 30 minutes, the mixture was returned to room temperature and the solvent was distilled off under reduced pressure to obtain isopropyl N-(3-chloro-4-ethoxy-5-isocya-11 phenyl)carbamate. Without purification, this was added dropwise to a 50-ml toluene bath solution containing 1.0 g of triethylamine and 0.64 f of allyl alcohol at room temperature. After being left at room temperature for 12 hours, it was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography using a mixed solvent of toluene and ethyl acetate.
8.65% of 3-chloro-4-ethoxy-5-allyloxycarbonylaminophenyl)carbamate was obtained. (
Yield 98.8%) n"91.5320 Example 5 [According to manufacturing method (e)] Sodium hydride 0.1071 (60% oily) was mixed with N,
It was suspended in 20 m6 of N-dimethylformamide, and 0.80 g of isopropyl N-(3-nitro-4-hydroxy-5-methoxycarbonylphenyl) carbamate was added to the suspension under water cooling. After stirring the reaction solution at room temperature for 1 hour, 0.50 F of ethyl iodide was added thereto at room temperature.

After stirring at 90°C for 30 minutes, the reaction solution was poured into ice water.
Extracted with ethyl acetate. The organic layer was washed with water and dried over magnesium sulfate.

The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography using a mixed solvent of toluene and ethyl acetate.
-Ethoxy-5-methoxycarbonylphenyl)carbamate [Compound No. (5)] 0.77 f was obtained.

(Yield: 88.6%) m, p, 117-120°C Table 1 shows examples of the Kibaho compounds thus obtained.

When actually applying the compound of the present invention obtained in this way, it can be used as it is without adding other ingredients, or it can be mixed with a carrier to make it easier to use as a fungicide. For example, it is formulated into powders, wettable powders, oils, emulsions, tablets, granules, fine granules, aerosols, flowables, and the like.

Examples of formulations are shown below.

Formulation Example 1 Powder 2 parts of the compound of the present invention (1), 88 parts of clay, and 1 part of talc
Part θ is thoroughly ground and mixed to obtain a powder having a base ingredient content of 2%.

Formulation Example 2 Wettable powder 30 parts of the compound of the present invention (2), 45 parts of diatomaceous earth, 20 parts of white carbon, 8 parts of a wetting agent (sodium lauryl sulfate) and 2 parts of a dispersing agent (calcium lignin sulfonate) were thoroughly ground and mixed. A hydrating agent with a base ingredient content of 30% is obtained.

Formulation Example 3 Wettable powder Compound of the present invention (8) 50 parts, diatomaceous earth 45 parts, wet +11
5 agents (calcium alkylbenzenesulfonate) 2.
Part 5'! ' and 2.5 parts of a dispersant (calcium lignin sulfonate) were sprinkled and pulverized and mixed to obtain a wettable powder having a base ingredient content of 50%.

Formulation Example 4 Emulsion A log compound of the present invention (4), 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%.

The above formulations generally contain from 1.0 to 1.0% by weight of active compound.
95.0%, preferably 2.0 to 80.0%, and the application rate is usually 10 to 1 ooy per 10 are. Furthermore, the concentration used is preferably in the range of 0.005 to 0.5%, but the amount and concentration used depend on the dosage form, application period,
Methods, locations, target diseases, target crops, etc. (as these also vary, there is no problem in increasing or decreasing the amount without being limited to the above range.

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

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

Note that the control compounds are indicated by the common names shown in Table 2.

Table 2 Note (1) Commercial herbicide Note (2) Commercial fungicide test example 1
Cucumber powdery mildew control effect Fill a 90-capacity plastic pot with sandy loam and grow cucumbers (variety: Sumo Half-day)
was sown. This was cultivated at room temperature for 8 days to obtain cucumber seedlings with expanded cotyledons. A water-diluted solution of an emulsion of the compound of the present invention below and a hydrating powder of a control compound prepared according to Formulation Example 4 was sprayed on the seedlings until a sufficient amount of droplets adhered to the leaf surface.

After air-drying the chemical solution, seedlings are exposed to chemical-resistant or sensitive cues.
'5phaerotheca ful
A conidial suspension of M. iginea was inoculated by spraying. After cultivating this in a greenhouse for 10 days to develop disease, the disease state was observed.

The disease severity was calculated by 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.

(Sickness index) (Sickness status) 0...
... No bacterial flora or lesions observed on the leaf surface.

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

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

2. M plexus or lesions are observed on the leaf surface in less than 50% of the leaf area.

4 ・・・・・・・・・ Bacterial flora or lesions are observed on the leaf surface over 50% or more of the leaf area.

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

As a result, as shown in Table 3, the compound of the present invention showed an excellent control effect when inoculated with drug-resistant bacteria, but did not show a control effect when inoculated with drug-susceptible bacteria. - None of the commercially available fungicides benomyl, thiophanate methyl, and carpendazim showed a control effect when inoculated with drug-resistant bacteria, but showed an excellent control effect when inoculated with drug-susceptible bacteria.

Commercially available herbicides with similar chemical structures showed almost no control effect when inoculated with any of the bacteria.

Table 3 Test Example 2 Sugar beet brown spot control effect A 90-volume plastic pot was filled with sandy loam, and sugar beet (variety: Tetroit Dark Red) was sown. Formulation Example 4 was applied to seedlings obtained after 20 days of cultivation in a greenhouse.
A water-diluted solution of an emulsion of the compound of the present invention and a hydrating powder of a control compound prepared in accordance with the following was sprayed on foliage until the droplets sufficiently adhered to the leaf surface. After air-drying the chemical solution, seedlings were infected with drug-resistant or susceptible sugar beet brown spot (C1ercospora b).
eticola) (y) Conidial suspension tig inoculated. This was covered with a vinyl cover to create humid conditions, and after cultivating in a greenhouse for 10 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 shown in Table 4, similar to the results of Test Example 1, the compounds of the present invention exhibited excellent control effects when inoculated with drug-resistant bacteria, whereas the commercially available fungicides benomyl, thiophanate methyl, and carpendazim showed drug-resistant bacteria. It shows excellent control effects when inoculated with bacteria. Commercially available herbicides with similar chemical structures show almost no control effect when inoculated with any of the bacteria.

Table 4 Test Example 3 Pear scab control effect A 90-capacity plastic pot was filled with a mixed soil of peat moss and sandy loam, and seeds collected from pear fruits (variety: Nagakobu) were sown.

This was cultivated in a greenhouse for 20 days, and a water diluted solution of an emulsion of the compound of the present invention prepared according to Formulation Example 4 below and a hydrating powder of the control compound below was applied to the resulting seedlings until the droplets sufficiently adhered to the leaf surface. Sprayed on foliage.

After air-drying the chemical solution, the seedlings were inoculated by spraying with a conidial suspension of Venturia nashicola, which is resistant or susceptible to the drug. The plants were placed under humid conditions at 20°C for 3 days, and then cultivated under fluorescent lamp illumination at 20°C for 20 days to develop the disease.

The method of measuring the onset of disease and the calculation of control value were the same as in Test Example 1.

As a result, as shown in Table 5, the compounds of the present invention showed excellent control effects when inoculated with drug-resistant bacteria, and conversely, the commercially available fungicides henomyl and thiophanate methyl showed excellent control effects when inoculated with drug-susceptible bacteria. Indicated.

Table 5 Test Example 4 Effect on controlling bean nut brown spot disease Fill a 100-cup plastic pot with sandy loam, and sow 1 bean nut (variety: Nichiba Hantachi). In the greenhouse 1
After 4 days of cultivation, the seedlings obtained were sprayed with a water diluted solution of an emulsion of the compound of the present invention below prepared according to Formulation Example 4 and a hydrating powder of the control compound below at 10 times per pot. After air-drying the chemical solution, the young samurai was infected with a drug-resistant or susceptible peanut brown spot bacterium (Cercospora arachi).
A total of 1 liter of the spore suspension of A. la) was inoculated with mist.

After cultivating it in a greenhouse for 10 days under humid conditions by covering it with a hinyl power bar, the state of disease development 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 6, the compounds of the present invention showed excellent control effects when inoculated with drug-resistant bacteria, and conversely, the commercially available fungicides benomyl and thiophanate methyl showed excellent control effects when inoculated with drug-susceptible bacteria. Indicated.

Table 6 Test N5 Control effect on botrytis gray mold on cucumber A 90 ml plastic pot was filled with sandy loam, and cucumbers (variety: Aigoku Half Day) were sown. Cultivate this in a greenhouse for 8 days,
The cotyledons were spread and a water diluted solution of a hydrating powder of the following control compound was applied to the pot. After air-drying the chemical solution, seedlings were infected with chemical-resistant or sensitive cucumber gray mold fungi (, B
otrytis cinerea) was pasted onto the leaf surface and inoculated.

The plants were placed in a humid environment at 20° C. for 3 days to develop disease, and then the state of disease development 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 7, the compounds of the present invention showed excellent control effects when inoculated with drug-resistant bacteria, and conversely, the commercially available fungicides benomyl and thiophanate methyl showed excellent control effects when inoculated with drug-susceptible bacteria. Indicated.

Table 7 Test Example 6 Effect on controlling cucumber vine blight A 90-volume plastic pot was filled with sandy loam, and cucumbers (variety: Aigoku Half Day) were sown. This was cultivated in a greenhouse for 8 days to obtain cucumbers with expanded cotyledons. To these seedlings, a water diluted solution of an emulsion of the compound of the present invention below prepared according to Formulation Example 4 and a hydrating powder of the control compound below was added to each pot.
0-1 sprayed on foliage. After air-drying the chemical solution, seedlings are infected with chemical-resistant or sensitive cucumber vine blight fungus (Myc'osphae).
Rella melonis) bacterial flora cutting plate (diameter 5
m) was pasted on the leaf surface and inoculated. This at 20℃
After leaving the device under humid conditions for 3 days to induce disease, the state of disease onset 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 8, the compound of the present invention showed an excellent control effect when inoculated with drug-resistant bacteria, and conversely, the commercially available fungicides benomyl and thiophanate methyl showed excellent control effects when inoculated with drug-susceptible bacteria. Ta.

Table 8 Test Example 7 Citrus Blue Mold Control Effect Epsilon Kan fruit (variety: Unshu) was thoroughly washed with water and air-dried.
The following emulsion of the present compound prepared according to Formulation Example 4 and the following control commercially available drug were diluted with water and immersed in a drug solution of a predetermined concentration for 1 minute.

After air-drying, the drug-resistant or susceptible tangerine blue fungus (P
enicilljum italicum) conidia were suspended in water and sprayed onto the fruit surface.

After being placed in a moist room for 14 days after being covered, the degree of disease onset was investigated using the disease index of 0.1.2.3.4.5 as shown below.

(Disease condition) (Infection index) No lesions observed 0 Lesions observed on less than 20% of the fruit surface area l〃 2
Lesions are observed in less than 0-40% 2 40-6
0% 〃 3〃 60-80%
4. Lesions are observed in 80% or more. 5. The disease severity and control value were calculated in the same manner as in Test Example 1.

As a result, as shown in Table 9, the compound of the present invention showed an excellent control effect when inoculated with drug-resistant bacteria, and conversely, the commercially available fungicides baremil and thiophanate methyl showed excellent control effects when inoculated with drug-susceptible bacteria. tco.

Table 9 Test Example 8 Phytotoxicity test on crops A 150 ml plastic pot was filled with sandy loam.
Wheat (variety: Norin No. 61), apple (variety: Kogyoku),
Sow each type of Beanatsu (variety: Chiba erect),
Grown in a greenhouse. A water diluted solution of an emulsion of the compound of the present invention below and a hydrating powder of the control compound below, prepared according to Formulation Example 4, was sprayed on the stems and leaves of the obtained seedlings.

After spraying, the plants were placed in the greenhouse again, and after cultivation for 10 days, the presence or absence of phytotoxicity was investigated according to the following criteria.

Standards for degree of drug damage (Severity) (Symptoms) -No abnormality.

10. Abnormalities due to chemical damage are observed in some of the crops.

Park: Abnormalities due to chemical damage are observed throughout the crop.

■ The plant will wither and die due to chemical damage.

As a result, as is clear from Table 10, the compound of the present invention had no harmful effect on crops, while the commercially available herbicide with a chemical structure similar to that used as a control had a phytotoxic effect.

Table 10 161104 7144-4 H@
Inventor: Sube Kato, 4-2-1 Takashi, Takarazuka City, Sumitomo Chemical Co., Ltd. Inventor: Yuji Noguchi, 4-2-1 Takashi, Takarazuka City, Sumitomo Chemical Co., Ltd.: Yukio Oguri, Takarazuka City 4-2-1 Takashi Sumitomo Chemical Co., Ltd. Author Shigeo Yamamoto 4-2-1 Takashi, Takarazuka City Sumitomo Chemical Co., Ltd. 0 author Author Katsuzo Kamoshita 4-2-1 Takashi, Takarazuka City Amendment to internal proceedings of Sumitomo Chemical Co., Ltd. (spontaneous) February 17, 1980 Kazuo Wakasugi, Commissioner of the Patent Office 1. Indication of the case 1988 Patent Application No. 218512 2. Title of invention: Aniline derivatives, production thereof Law and agricultural and horticultural fungicide 3 containing the same as an effective ingredient, and its relationship to the amended case Patent applicant address 5-15 Kitahama, Higashi-ku, Osaka Name (
209) Sumitomo Chemical Co., Ltd. Representative Hijikata
Takeshi 4, agent address: 5-15 Kitahama, Higashi-ku, Osaka, Schiff 4) 5. 5. Detailed explanation of the invention in the subject specification of m-positive, Iran 6. Contents of amendment (1) Table 1 A on page 46 of the specification, compound number (1)
In the R1 column of 7), correct l'-CH2j to rCH3j.

(2) J 1.7 B (q, 2H,) J in the physical agility fixed failure column of compound number (42) in Table 1 on page 50
``6.50J, respectively [2, t a (t
, 2D) J, [7,,50J is corrected.

that's all

Claims (9)

[Claims] (1) General formula [I] [wherein, X is a nitro group, an amino group, a thioisocyanato group, or a group represented by the general formula (Here, A'' and A'' are the same or different and represent an oxygen atom or a sulfur atom, and R2 is a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower haloalkyl group or (represents a lower alkoxyalkyl group). Y represents a lower alkyl group, a lower alkoxyl group, a lower alkoxycarbonyl group, a hydrogen atom, a halogen i atom, or an acyl group. R1 represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, Represents a lower haloalkyl group, lower alkoxyalkyl group, lower cycloalkylalkyl group, or lower cyanoalkyl 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 Represents a substituent represented by the general formula -W-18 (where W represents an oxygen atom or a sulfur atom, and Ra represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower haloalkenyl group, a lower haloalkynyl group) or represents a lower cycloalkyl group, or represents a phenyl group optionally substituted with a haloken atom, or represents a halogen atom, a cyano group, a phenyl group, a lower cycloalkyl group, a lower alkoxyl group, a lower alkenyloxy group, a lower A haloalkoxy group, a phenoxy group or an aralkyloxy group represents an alkyl group substituted with at least one atom or a group. (2) The aniline derivative according to claim 1, wherein in the general formula [1], the substituent Y represents a lower alkyl group, a lower alkoxyl group, a lower alkoxycarbonyl group, a halogen atom, or an acyl group. (3) In Kamifune general formula [I], the substituent X represents a general group, where A' and A'' are the same or different and represent an oxygen atom or a sulfur atom, and the latter represents a lower alkyl group. ), Y represents a lower alkyl group, a lower alkoxyl group, a halogen atom, or an acyl group, and Y represents a lower alkyl group, a lower alkenyl group, a lower aquinyl group, a lower haloalkyl group, a lower alkoxyalkyl group, or a lower cyano group. The aniline derivative according to claim 1, wherein R8 when alkyl represents a lower alkyl group. (4) General formula [wherein, (Y represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower haloalkyl group, or a lower alkoxyalkyl group.) Y represents a lower alkyl group, a lower alkoxyl group, a lower alkoxycarbonyl group, Represents a hydrogen atom, a halogen atom, or an acyl group.Rr is a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower haloalkyl group, a lower alkoxyalkyl group, a lower cycloalkylalkyl group -t
y represents a lower cyanoalkyl group. ] A compound represented by the general formula [wherein 2 represents a halogen atom]. A represents an oxygen atom or a sulfur atom. B represents a lower alkyl group, a lower alkenyl group, a lower cycloalkyl group, a phenyl group, or a substituent represented by the general formula -W-R8 (where W represents an oxygen atom or a sulfur atom, and R3 represents a lower alkyl group) , a lower alkenyl group, a lower alkynyl group, a lower haloalkenyl group, a lower haloalkynyl group or a lower cycloalkyl group, or a phenyl group optionally substituted with a halogen atom, a cyano a 1-alkyl group substituted with at least one atom or group of groups, phenyl i, lower cycloalkyl i, g-class alkoxyl group, lower alkynyl base group, lower haloalkoxy group, phenoxy group or aralkyloxy group 7J-Representation.]o] An aniline derivative represented by the general formula [wherein X, Y, R1, A and B have the same meanings as above], characterized by reacting with a compound represented by the following: manufacturing method. (5) General formula [wherein, (Here, A' and A'' are the same or different and represent an oxygen atom or a sulfur atom, R2 is a lower alkyl group,
Represents a lower alkenyl group, lower alkynyl M, lower haloalkyl group or lower alkoxyalkyl group. ). Y represents a lower alkyl group, a lower alkoxyl group, a lower alkoxycarbonyl group, a hydrogen atom, a halogen atom, or an acyl group.几1 represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower haloalkyl group, a lower alkoxyalkyl group, a lower cycloalkylalkyl group or a lower cyanoalkyl group. A represents an oxygen atom or a sulfur atom. ” and the general formula % formula % [wherein R8 is a lower alkyl group, a lower alkyl group,
Represents a lower alkynyl group, lower haloalkenyl group, lower cyloalkyl group or lower cycloalkyl group, but
This represents a phenyl group which may be substituted with a halogen atom, or a halogen atom, cyan group, phenyl group, lower cycloalkyl group, lower alkoxyl-i, lower alkenyloxy group, lower haloalkoxy group, phenoxy group, or It represents an alkyl group substituted with at least one atom or group among aralkyloxy groups. W represents an oxygen atom or a sulfur atom. ] In the general formula E, X, Y, Rt, Rg, A and W have the same meanings as above. ] A method for producing an aniline derivative represented by (6) General formula [wherein Y represents a lower alkyl group, a lower alkoxyl group, a lower alkoxycarbonyl group, a hydrogen atom, a halogen atom or an acyl group. R1 is a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower haloalkyl group,
Represents a lower alkoxyalkyl group, a lower cycloalkylalkyl group, or a lower cyanoalkyl group. A represents an oxygen atom or a sulfur atom. B represents a lower alkyl group, a lower alkenyl group, a lower cycloalkyl group, a phenyl group, or a substituent represented by the general formula -W-Rs (where W represents an oxygen atom or a sulfur atom, and R8 represents a lower alkyl group) , a lower alkenyl group, a lower alkynyl group, a lower haloalkenyl group, a 4fuEt haloalkynyl group or a lower cycloalkyl group, or a phenyl group which may be substituted with a halogen atom, or a halogen atom, a cyano group, phenyl &, lower cycloalkyl group, lower alkoxyl group, lower fluorenyloxy group, lower haloalkoxy group, phenoxy group (if this represents an alkyl group substituted with at least one atom or group among aralkyloxy groups). ] and the compound represented by the general formula % formula % [wherein, , ; Hl represents a lower alkyl group, lower alkenyl i, lower haloalkyl x, lower alkoxyalkyl group, or a group represented by the general formula =A''-R2 ( Here, A″ represents an oxygen atom or a sulfur atom, and 1lL2
represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower haloalkyl group or a lower alkoxyl group. ). A' represents an oxygen atom or a sulfur atom. Z
represents a halogen atom. ] A general formula characterized by reacting with a compound represented by [wherein Y, R1, A'2. A, A' and B have the same meanings as above. ] A method for producing an aniline derivative represented by: (7) General formula [wherein Y represents a lower alkyl group, a lower alkoxyl group, a lower alkoxycarbonyl group, a hydrogen atom, a halogen atom or an acyl group. 1 is a lower alkyl group, lower alkenyl x, lower alkynyl group, lower haloalkyl group,
Represents a lower alkoxyalkyl group, a lower cycloalkylalkyl group, or a lower cyanoalkyl group. A and A
' represents an oxygen atom or a sulfur atom. B represents a lower alkyl group, a lower alkenyl group, a lower cycloalkyl group, a phenyl group, or a substituent represented by the general formula -W-Rs (where W represents an oxygen atom or a sulfur atom, and R8 is Represents a lower alkyl group, 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 a halogen atom, Cyano group, phenyl group, lower cycloalkyl x, lower ylkoxyl group, lower alkenyloxy group, lower haloalkoxy group, phenoxy group represents an alkyl group substituted with at least one atom or group among aralkyloxy groups. ). ] A compound represented by the general formula % formula % [In the formula, loss represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower)\o 7 Jl/kyl group or a lower alkoxyl group, and A'' represents oxygen represents a sulfur atom or a sulfur atom.
and B have the same meanings as above. ] A method for producing an aniline derivative represented by (8) General formula [wherein, (Here, A' and A' are the same or different and represent an oxygen atom or a sulfur atom, R2 is a lower alkyl group,
A lower alkenyl group, a lower alkynyl group, a lower haloalkyl group represents a lower alkoxyalkyl group. ). Y represents a lower alkyl group, a lower alkoxyl group, a lower alkoxycarbonyl group, a hydrogen atom, a halogen atom, or an acyl group. A represents an oxygen atom or a sulfur atom. B represents a lower alkyl group, a lower alkenyl group, a lower cycloalkyl group, a phenyl group, or a substituent represented by the general formula -W-Re (where W represents an oxygen atom or a sulfur atom, and R8 represents a lower alkyl group) , a lower alkenyl group, a 4Fh alkynyl group, a lower haloalkenyl group, a lower haloalkynyl group represents a lower cycloalkyl group, or represents a phenyl group optionally substituted with a haloken atom, or a halokenyl atom. , a cyano group, a phenyl group, a lower cycloalkyl group, a lower alkoxyl group, a lower alkenyloxy group, a lower haloalkoxy group, a phenoxy group, or an aralkyloxy group. . ] A phenol derivative represented by the general formula [wherein is a lower alkyl group, a lower alkenyl M, a lower alkynyl group,
A lower 9 haloalkyl group, a lower alkoxyalkyl group, a lower cycloalkylalkyl group represents a lower cyanoalkyl group. D represents a halogen atom, mesyloxy group or tosyloxy group. [In the formula, X, Y, Rr, A and B represent the same meanings as above.] ] A method for producing an aniline derivative represented by (9) General formula [wherein, (wherein, A' and A' are the same or different and represent an oxygen atom or a sulfur atom, and R2 represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower haloalkyl group, or a lower alkoxyalkyl group). Y represents a lower alkyl group, a lower alkoxycarbonyl group, a lower alkoxycarbonyl group, a water atom, a halogen atom or an acyl group. R1 represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower haloalkyl group, a lower alkoxyalkyl group, a lower cycloalkylalkyl group or a lower cyanoalkyl 3° group. A represents one or more oxygen atoms and sulfur atoms. B represents a lower alkyl group, lower alkenyl M, lower 9 haloalkyl group, phenyl group, or a substituent represented by the general formula -W-8 (where W represents an oxygen atom or a sulfur atom, and Rs represents a lower alkyl group) group, 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 a halogen atom, a cyano group , a phenyl group, a lower cycloalkyl group, a lower alkoxyl group, a lower arykenyloxy group, a lower haloalkoxy group, a phenoxy group, or an aralkyloxy group. ] An agricultural and horticultural fungicide characterized by containing an aniline derivative represented by the following as an active ingredient.