JPS59184150A - Aniline derivative, its production and agricultural and horticultural germicide containing the same as active constituent - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (X and Y are halogen, H, lower alkyl, etc. provided that X and Y are not H at the same time; R1 is -CH2R3, -COR4 or -SO2R5; R3 is cyano, lower cyanoalkyl or lower alkylthio; R4 is lower alkyl, lower alkoxyl or lower alkylamino; R5 is lower alkyl, lower haloalkyl, etc.; Z is -W-R6; W is O or S; R6 is lower alkyl, lower alkenyl or lower alkynyl, etc.). EXAMPLE:Isopropyl N-( 3-chloro-4-methylcarbamoyloxy-5-methoxymethylphenyl ) carbamate. USE:An agricultural and horticultural germicide having selectively high germicidal activity against chemical resistant germs. PREPARATION:A compound expressed by formula II is reacted with a chloroformic acid ester expressed by formula III to give the aimed compound expressed by formula I .

Description

Detailed Description of the Invention The present invention relates to the general formula (I) [wherein x and y are the same or different, a halogen atom, a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a compound of the general formula
-CH2OR2, -000R2 represents the group represented.

Here, R2 represents a lower alkyl group. However, xY does not simultaneously represent a hydrogen atom. The tile □ indicates the general formula % formula % 0 group. Here, R3 represents a cyano group, a lower cyanoalkyl group, or a lower alkylthio group, R4 represents a lower alkyl group, a lower alkoxy group, or a lower alkylamino group, and R5 represents a lower alkyl group, a lower haloalkyl group, or a lower alkylamino group. show. 2 represents a group represented by the general formula -WR6. Here, W represents an oxygen atom or a sulfur atom, and R6 represents a lower T alkyl group, a lower alkenyl group, a lower alkynyl group, a lower haloalkyl group, or a lower alkoxyalkyl group. ] The present invention relates to an aniline derivative represented by the following, a method for producing the same, and an agricultural and horticultural fungicide characterized by containing the same as an active ingredient.

The N-7-enylcarbamate compounds represented by the general formula (1) are benomyl [methyl 1-(butylcarbamoyl)penzimitazol-2-ylcarbamate] and fuveridazole (2-(2-furyl)benzimidazole).
, thiabendazole (2-(4-thiazolyl)benzimidazole), carpendazim [methyl benzimidazol-2-yl carbamate], theofinatomethyl [1,2-bis(3-methoxycarbonyl-2-thiourido)benzene], thiophanate [ 1,2-bis(3-ethoxycafflevonyl-2-thioureido)benzene], and procymidone (N-(3', 5')).
-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide], iprodione (3
-(3', s'-cylorophenyl)-1-isopropylcarbamoylimitazolidine-2,4-dione],
Vinclozolin [3-(3',5'-dichlorophenyl)-5-methyl-5-vinyl-oxazolidine-2,4
-dione], ethyl (RS) -3-(s', s
'-dichlorophenyl)-5-methyl-2,4-dioxoxazolidine-5-carboxylate and other cyclic imide fungicides and other filamentous fungi (hereinafter referred to as drug-resistant bacteria) that exhibit resistance to cyclic imide fungicides such as , is characterized by a selectively strong bactericidal effect.

The present inventors have been working diligently to invent a fungicide with such properties because if there is a fungicide that selectively shows bactericidal effects against drug-resistant bacteria, it can be expected to have a high disease control effect in fields where drug resistance has occurred. I tried hard.

As a result, it was found that the above-mentioned N-phenylcarbamate compound is a bactericidal agent that exhibits a strong bactericidal effect selectively against drug-resistant bacteria. That is, as is clear from the test examples described below, the compounds of the present invention are not susceptible to diseases caused by wild bacteria (hereinafter referred to as drug-susceptible bacteria) that are susceptible to benzimidazole thiono-1nate fungicides or cyclic imide fungicides. However, the compound of the present invention showed an excellent control effect against diseases caused by drug-resistant bacteria, and the bactericidal activity of the compound 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 and thiononate fungicides; therefore, the above agents are used.
This can be used to control drug-resistant bacteria that are expected to emerge or have emerged. For example, powdery mildew of apples (Podosphaera 1eoucotrl)
cha), Venturia 1naequ
alis), black spot fungus (M7COp-ha, erell
a pomi), brown spot fungus (Mirssoninama)
Scl erot 1nia m
al i ), Kaki9 powdery mildew fungus (Phyllshc
tinia kakicola), anthracnose fungus (Gloe
osporium kaki), peach gray layer fungus (
Sclerotinisi cinerea), Cladosporium carpophilu
m), Phomopsis rot fungus (Phomops i)
s sp, ), botrytis fungus of grapes (Botry
tii cineresi)-1 ampel
ina), Glomerella cin
gulata), Cercasp
ora beticala), beach, %/cercospora arachidicolm
, Ercaipora persona (C)
t@), barley powdery mildew fungus (Erysiphe)
gramins f, sp.

horde, I-X pot disease fungus (Cercospo
rel laherpotrichoides),
・Fusarium nivale, wheat powdery mildew (ErySip) egramini
s f , sp , tritici ), cucumber powdery mildew fungus (Sphierotheca fuli
ginea), mycosphaerll
ameL6nis), Sclerotinia bacterium (Scl erot
i? scl erot iorum), Botrytis cinene, Botrytis sclera (Cl
adosporiumCuCuXner inum),
Tomato leaf mold fungus (C1, adosporium f
ulvum), Botrytis ci
nerea), eggplant black blight fungus (Corynespor)
a melongenae), a powdery mildew fungus of strawberries.
(Sphaerotheca humul i), Fusarium oxysporum f,
sp, fragariae), onion gray rot fungus (Botrytii alli), and lettuce sclerotium fungus (Botrytii alli).
Sclerotinia sclerotiorum)
, Cercospara api
i) Phaeoisari
opsls ga■-eoia), hop Botrytiscinerea, Tahakono powdery mildew (Erysiphecichor@cearu)
m), Diplocsirpmro
sae), tangerine scab fungus (Elsinae f.
ay-cetti), blue mold fungus (Penicilli)
um italicum), green mold fungus (Penici
It can be used to control drug-resistant bacteria such as llium digitatum).

As a result of further studies, it was found that the compounds of the present invention are effective in controlling rice blast fungi (Pyriculiris Lory$ae) and the like, regardless of the presence or absence of drug resistance. .

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

(-1 general formula (II) [In the formula, X, Y, and have the same meanings as above.

] A compound represented by the general formula [wherein Z has the same meaning as above. A manufacturing method that involves reacting with a chloroformic acid ester shown in ].

This reaction is carried out in an organic solvent such as benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, chloroform, carbon tetrahydride, ethyl acetate, pyridine, dimethylformamide, or a mixture thereof; pyridine, triethylamine, N, By using a dehydrochlorination agent such as N-diethylaniline, sodium hydroxide, potassium hydroxide, etc., the reaction can be carried out in high yield.

The reaction is cooled or heated (0 to 150°C) as necessary.
By doing so, the reaction can be completed in an instant to 10 hours, and the desired product can be obtained in good yield.

(b), general formula (m) [In the formula, X, Y and Ni have the same meanings as above.

] A phenyl isocyanate derivative represented by the general formula [wherein 2 has the same meaning as above]. ] A production method of reacting with an alcohol or thioalcohol.

This reaction is carried out without a solvent or in an organic solvent such as benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, N,N-dimethylformamide, chloroform, carbon tetrachloride, etc., without a catalyst, or with triethylamine, N,N-diethylaniline, This can be carried out using 1,4-diazabicyclo-(2,2,2)-octa7 as a catalyst.

By cooling or heating (0 to 50° C.) as necessary, the reaction can be completed instantly to 10 hours and the desired product can be obtained in good yield.

The phenyl isocyanate derivative represented by the general formula (m) can be obtained by reacting the a-neelin derivative represented by the general formula (I[) with phosgene.

This reaction is carried out in an organic solvent such as benzene, toluene, xylene, ethyl acetate or a mixture thereof. The reaction can be carried out by heating from 50°C to reflux temperature as necessary.
The process can be completed in 10 hours rather than instantaneously, and the desired product can be obtained in good yield.

C) General formula (IV) [In the formula, X, Y and 2 are as described above. ] A phenol derivative represented by the general formula
and R7 are as described above. ] A manufacturing method of reacting with a compound represented by:

Here, R7 is a leaving group such as a halogen atom or a mesyloxy group.

- This reaction can be carried out without a solvent, or in water, or an organic solvent such as benzene, toluene, tetrahydrofuran, dimethyl sulfoxide, or dimethyl formamide. Alternatively, by using sodium hydroxide, potassium carbonate, sodium hydride, etc., the desired product can be obtained in a high yield.
The reaction time is 30 minutes to 12 hours.

The phenol derivative represented by the general formula (IV) is represented by the general formula (V) [wherein, X and Y are as described above]. ] and a 4-aminophenol derivative represented by the general formula [■] [wherein Z is as described above]. ] [In the formula, x # and Y are As mentioned above. ]-4-hydroxyphenylisocyanate derivative represented by
It can be obtained by a method of reacting with an alcohol or thioalcohol represented by the general formula [■] Z -H (■) [wherein 2 is as described above].

The condensation reaction between the 4-aminophenol derivative of the general formula [■] and the chloroformate ester of the general formula (VI) can be carried out using benzene, toluene, xylene, diethylethyl, tetrahydrofuran, dioxane, chloroform, carbon tetrachloride,
The reaction is carried out in an organic solvent such as ethyl acetate, pyridine, dimethylformamide, or a mixture thereof, and by using a dehydrochlorination agent such as pyridine, triethylamine, N,N-diethylaniline, sodium hydroxide, potassium hydroxide, etc. can be carried out with high yield. The reaction can be completed in an instant to 10 hours by cooling or heating (0 to 150° C.) as necessary, and the desired product can be obtained in a high yield.

The reaction between the 4-aminophenol derivative of general formula (V) and phosgene is carried out in an organic solvent such as benzene, toluene, ethyl acetate, or a mixture thereof. The reaction is carried out at a temperature ranging from 50 DEG C. to reflux, if necessary, and is completed in 30 minutes to 10 hours, and the 4-hydroxyphenylisocyanate conductor of the general formula [■] can be obtained in good yield.

The condensation reaction between the compound of general formula [■] and the alcohol or thioalcohol of general formula [■] can be carried out without a solvent or with toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, N,N-dimethylformamide, chloroform, The reaction can be carried out in an organic solvent such as carbon chloride without a catalyst or with triethylamine, N,N-diethylaniline, or 1°4-diazabicyclo-(2,2,2)-octane as a catalyst.

The reaction can be completed instantaneously to 10 hours by cooling or heating (0 to 50° C.) as necessary, and the phenol derivative of the general formula (IVI) can be obtained in good yield.

The 4-aminophenol derivative (V), which is a starting material, has the general formula (IX) [wherein X and Y are as described above]. ] It can be obtained by the reduction reaction of the 4-nitrophenol derivative shown below. For example, it can be obtained by hydrogenating compound (IX) in an organic solvent such as ethanol or ethyl acetate using a catalyst such as platinum dioxide or palladium on carbon at a temperature of 0°C to 60°C under normal pressure or increased pressure. 4-Nitrophenol derivative [IX) is described in Reference J, Org, Chem, 27
, 218 (1962).

Next, examples of the compounds of the present invention represented by the general formula CI) are as follows, but the compounds of the present invention are not limited to these numbers. Note that the compound numbers shown here are commonly used in the following formulation examples and test examples.

Next, examples will be shown.

Example 1 Synthesis of isopropyl N-(3-chloro-4-methylcarbamoyloxy-5-methoxymethylphenyl)carbamate. (According to method (a).) 3-Rio-4-methylcarbamoyloxy-5
-Methoxymethylaniline 1.02 and N,N-diethylaniline 0.90 fI were dissolved in toluene 15-, and isopropyl chloroformate 0.759 was dissolved under water cooling.
It was dripped in minutes.

After being left at room temperature for 12 hours, it was poured into ice water and extracted with ethyl acetate. The solvent 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 chromatography using a mixed solvent of benzene and tetrahydrofuran to obtain isopropyl N-(3-chloro-
1.229 of 4-methylcarbamoyloxy-5-methoxymethylphenyl)carbamate was obtained. (Yield 9o
, 5%) Melting point 113-114℃ Elemental analysis value N%) 0%) H%) C/$
) Calculated value 8.47 50.84 5.79 10
．． 72 (as C14H19N2CI!05) Actual value
8.35 50.81 5.88 10.92 Example 2 Synthesis of isopropyl N-[3-chloro-4-(3-cyanobrobyloxy)-5-methoxymethylphenyl]carbamate. (No. 74(b)) 3-chloro-4-(3-cyanopropyloxy)-5-
Methoxymethylaniline 2.55 F to toluene 20-
and add 10~ to a toluene solution containing 101 phosgene.
It was added dropwise at 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. Here, 2.809 of 3-chloro-4-(3-cyanopropyloxy)-51methoxymethylphenyl isocyanate was obtained. Without purification, 1.0% of triethylamine was added to isopro-lua A.
t Call 1. The mixture was added dropwise to a toluene solution of 50-. After leaving it at room temperature for 12 hours, put it in an ice bath,
Extracted with ethyl acetate. The solvent was washed with water and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting oil was purified by silica gel chromatography using a mixed solvent of toluene and ethyl acetate to obtain isopropyl N-[3-chloro-4-(3-cyanopropyloxy)-5-methoxy]. 2.70 grams of methylphenyl]carbame were obtained.

C yield 79.2'f6) Physical constant n20"1.5
1.98NMRδ(CDC/2s) 7.42(d,
in) *7.12(d, IH).

6.77 (br02Ld, IH).

4.92 (m, in), 4.45 (1,2H).

3.95 (t, 2H), 3.37 (1,3H)
.

2.65 (t, 2H), 2.18 (m, 2H
) tl, 25(d, 6H) Example 3 Synthesis of isopropyl N-(3-chloro-4-dianomethoxy-5-methoxymethyl phenyl)carbamate. (According to method (C)) 3-chloro-4-hydroxy-5-meth)-oxymethylaniline 52.8 PlN,N
-diethylaniline42. Of was dissolved in ethyl acetate. Here is isopropyl chloroformate 84.
69 was added dropwise over 15 minutes while cooling with water.

After being left at room temperature for 12 hours, it was poured into ice water.

The organic layer was washed with 10% hydrochloric acid and water, and dried over 7gnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography using a mixed solvent of toluene and ethyl acetate. Here, isopropyl N-
65.69 of (3-chloro-4-hydroxy-5-methoxymethylphenyl)carbamate was obtained.

Mix 240% dimethylformamide, 9.60F sodium hydride (60% oil) and 1,
Isopropyl N-(3-chloro1.rho4-
65.69 liters of hydroxy 5-methoxymethylphenyl) carbamate were added.

After further stirring at 20°C for 30 minutes, chloroacetonitrile 19. OF was added dropwise over 5 minutes. Heat it up,
After stirring at 90°C for 10 minutes, the mixture was poured into ice water and extracted with ethyl acetate. The solvent was washed with an aqueous potassium carbonate solution, water, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography using a mixed solvent of toluene and ethyl acetate to obtain isopropyl N-(3-chloro-4-cyanomethoxy-5-
White crystals of methoxymethylphenyl) carbamate 67
．． Obtained 5 F. (Yield 76.8%) Melting point 58
．． 5 to 60.5℃ Elemental analysis value, N loose) 0%) H (%) CJ (%) calculated value 8
．． 96 53.77 5.48 11.34 (014H
1γN2°, CZ) Actual value 8.88 53.77 5.57 11.6
Example 4 Synthesis of isopropyl N-(3-methyl-4-methylthiomethyloxy-5-n-propylphenyl)carbamate according to method (C). ) 1.65F of 3-methy)cy4-hydroxy-5-n-propylaniline was dissolved in 2° of ethyl acetate, phosgene, 1. It was added dropwise to an ethyl acetate solution containing Of- at 0 to 5°C. The mixture was heated gradually, and after changing from a cloudy state to a transparent state, the mixture was returned to room temperature, and the solvent was distilled off under reduced pressure. Here, 3-methyl-4-hydroxy-5-n-propylphenyl isocyanate was obtained.

Without purification, this was mixed with 1. Of triethylamine and 1. Of isopropyl alcohol. It was added dropwise to a toluene solution of 50% containing Of. After leaving it at room temperature for 12 hours, place it on ice.
It was poured into water and extracted with vinegar and ethyl acid. The solvent was washed with dilute hydrochloric acid and water, dried over magnesium sulfate, and evaporated under reduced pressure. The obtained residue was purified by silica gel chromatography using a mixed solvent of toluene and ethyl acetate to obtain 1.70 f of isopropyl N-(3-methyl 4-hydroxy-5-n-n-propylphenyl) carbamate.
l! the law of nature.

Sodium hydride (
60% oily) 0.28 fi and at 5° C. or lower, isopropyl N-(3-methyl-4-hydroxy-5-n-propylphenyl)carbame) 1.
709 Woffi added. Stir further at 20°C for 30 minutes, then chloro, methyl methyl sulfide 0.67
Added F. After heating and stirring at 90°C for 10 minutes, the mixture was poured into an ice bath and extracted with ethyl acetate. The solvent was washed with an aqueous potassium carbonate solution and water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure.The resulting residue was purified by silica gel chromatography using a mixed solvent of toluene and ethyl acetate. Isopropyl N2(3-methyl-4-methylthiomethyloxy-5-n-n-propylphenyl)carbamate 1.90F was obtained. (Yield
61.0%) Physical constant n; 1°' 1.5299N
MRa (CDCI!a) 7, Q l(s,
2H) #Q, 45 (broad, IH).

4.99 (nl, IH), 4.86 (s, 2H).

2.65 (t, 2H), 2.35 (fi, 3H)
.

2.34 (e3H), 1.29 (d, 6a).

0.80-1. ．． 50 (Product, 5H) When actually applying the compound of the present invention obtained in this way, it can be used in pure form without adding other ingredients, or it can be mixed with a carrier to make it easier to use as a fungicide. It can be applied in commonly used forms such as powders, wettable powders, oils, emulsions, tablets, granules, fine granules, aerosols,
It can be used as a floorable, etc.

Since the compound of the present invention shows high bactericidal activity selectively only against drug-resistant bacteria, it can be used alone when only drug-resistant bacteria are present, but when drug-sensitive wild bacteria are present, it can be used alone. It is preferable to use the above-mentioned benzimidazole thiono-1 nate fungicide or 1 in combination with the cyclic imide fungicide, or to use them alternately.

The active compounds (including mixed ingredients) are generally present in said preparations.
1.0 to 95.0%, preferably 2.0 to 95.0% by weight
Contains 80.0%, usually 10 to 100 per 10 ares
The application amount of v is appropriate. Furthermore, the concentration used is 0.0
A range of 0.5% to 0.5% is desirable, but the amount and concentration used vary depending on the dosage form, application time, method, location, target disease, target crop, etc., so it is not limited to the above range. There is no problem with increasing or decreasing it.

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

Next, test examples and formulations will be given to further clarify the usefulness of the compounds of the present invention as agricultural and horticultural fungicides.

Test Example 1 Cucumber Powdery Mildew Control Effect A 90-capacity plastic pot was filled with sandy loam, and cucumbers (variety:
Sumo Hanpaku) was sown. This was cultivated at room temperature for 8 days to obtain cucumber seedlings with expanded cotyledons. A water-diluted solution of the test compound in the form of an emulsion or a wettable powder was sprayed on the foliage of the seedlings until a sufficient amount of droplets adhered to the leaf surface. After air-drying the chemical solution, seedlings were infected with chemical-resistant or sensitive cucumber powdery mildew fungus (Sphλ).
A conidial suspension of erothet, aful 1g1nea) was inoculated by spraying. The plants were placed in a greenhouse and cultivated for 10 days to develop the disease, and then 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,
The disease was classified into indexes of 1, 2, and 4, and the disease severity was calculated using the following formula.

(Incidence index) (Infection 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 squares of the leaf area.

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

2... Bacterial flora and lesions are observed on the leaf surface in less than 50 square inches 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 2, the compound of the present invention showed an excellent control effect when inoculated with drug-resistant bacteria, but did not show any control effect when inoculated with drug-susceptible bacteria. - None of the commercially available fungicides Benomi, thiophanate methyl, and carpendazim showed any control effect when inoculated with drug-resistant bacteria, but showed excellent control effects when inoculated with drug-susceptible bacteria. .

Commercially available herbicides with similar chemical structures did not show any prevention or eradication effects when inoculated with any of the bacteria.

Table 2 Note (1) Commercially available herbicide Sweep Note (21e CIPC (Chlorobleph 1m) Note (
3) Barpan Note (41p CEPC: Note 15) tt IPC (Profam) Note 1
61 # BCPC (chlorbufam) Note (
7) 5- Commercially available fungicide Benomyl Note ↓ 8) # Thione mononate methyl Note (9)〃
Carpendazim Test Example 2 Sugar beet brown spot control effect A 90-capacity plastic pot was filled with sandy loam soil and sugar beet (variety:
Detroit Dark Crest) was sown. After 20 days of cultivation in a greenhouse, the resulting seedlings were sprayed with a water-diluted solution of the test compound in the form of an emulsion or wettable powder until the droplets sufficiently adhered to the leaf surface. After air-drying the chemical solution, young seedlings were infected with drug-resistant or susceptible sugar beet brown spot fungus (Cercospora beti).
colm) was inoculated by spraying with a conidial suspension. Cover this with a vinyl cover to create a humid condition, and put it in a greenhouse.
After cultivating for 0 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 3, similar to the results of Test Example 1, the compound of the present invention exhibited an excellent control effect when inoculated with drug-resistant bacteria; Carpendazim showed excellent control effects when inoculated with drug-susceptible bacteria. Commercially available herbicides with similar chemical structures rarely showed any control effect when inoculated with any of the bacteria.

Table 3 Note (3)〃 Perpan Note (41/l CEPC Note (9)〃 Carpendazim Test Example 3 Pear Scottle Control Effect A 90-capacity plastic pot was filled with a mixed soil of peat moss and sandy loam, and pear fruits were grown. (Cultivar: Chojube) and sowed the seeds.

This was cultivated in a greenhouse for 20 days, and a water diluted solution of the test compound in the form of an emulsion or wettable powder was sprayed on the foliage of the seedlings until the droplets sufficiently adhered to the leaf surface.

Drug-resistant or susceptible pear scab after air-drying with chemical solution -
A conidial suspension of Venturia nashicola was inoculated by spraying. The plants were placed under humid conditions at 20°C for 3 days, and then cultivated under fluorescent light for 201 days to develop the disease.

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

As a result, as shown in Table 4, 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. Ta.

Table 4 Note (2)〃 Thiophanate Methyl Test Example 4 Effect on Peanut Brown Spot Disease Control A 100-capacity plastic pot was filled with sandy loam, and peanuts (variety Nichiba semi-erect) were added.
was sown. After cultivation in a greenhouse for 14 days, a water diluted solution of the test compound in the form of an emulsion or a wettable powder was sprayed on the stems and leaves at 10 doses per pot. After air-drying the chemical solution, seedlings are infected with drug-resistant or susceptible peanut brown spot fungus (Cerc
ompora arachidicol λ) was inoculated by spraying. After cultivating the plants in a greenhouse for 10 days under humid conditions by covering them with a vinyl cover, the state of disease onset was observed. The onset of the disease, the investigation method, and the calculation of control value were carried out in the same manner as in Test Example 1.

As a result, the compounds of the present invention shown in Table 5 showed excellent control effects when inoculated with drug-resistant bacteria, and conversely, the commercially available fungicides benomyl and thiono-1 nate-methyl showed excellent control effects when inoculated with drug-susceptible bacteria. It showed a pesticidal effect.

Table 5 Note (1) Commercially available fungicide Benomyl Note (2) Methyl thiononate Test Example 5
Cucumber gray mold control effect Cucumbers (variety: Sumo Hanshiro) were sown in 90-volume plastic pots filled with sandy loam. This was cultivated in a greenhouse for 8 days to obtain cucumbers with expanded cotyledons. A water diluted solution of the test compound in the form of an emulsion or wettable powder is applied to the seedlings at 10 times per pot.
Sprayed on foliage. After the chemical solution is air-dried, the seedlings are infected with chemical-resistant or sensitive cucumber gray mold fungus (Batrytis cin).
ered) was inoculated by pasting a bacterial lawn cutting plate (diameter 5 mm) on the leaf surface. This was weighed under humid conditions at 20° C. for 3 days to induce disease, and then 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 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 thiono-1 nate-methyl showed excellent control effects when inoculated with drug-susceptible bacteria. It was shown to be effective.

Table 6 Note (1) Commercially available fungicide Benomyl Note (2) Thiono 1 nate methyl Test Example 6 Cucumber vine blight control effect A 90-volume plastic pot was filled with sandy loam and cucumbers (variety: Sumo Hanshiro) was sown. This was cultivated in a greenhouse for 8 days to obtain cucumbers with expanded cotyledons. A water-cooled solution of the test compound in the form of an emulsion or a wettable powder was applied to the seedlings at 10 times per pot and sprayed on the foliage. After air-drying the chemical solution, seedlings are infected with drug-resistant or sensitive cucumber vine blight fungus (Mycosphaerella).
melonis) was inoculated by pasting a bacterial lawn cutting plate (diameter 511 II) on the leaf surface. This was molded under humid conditions at 20° C. for 3 days to develop the 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, when compound 6 of the present invention was inoculated with drug-resistant bacteria, it showed an excellent control effect, and on the other hand, when commercially available fungicides benomyl and thiophanate methyl were inoculated with drug-susceptible bacteria, it showed an excellent control effect. showed that.

Table 7 Note (1) Commercially available fungicide Benomyl Note (2) Thioph7ate methyl Test Example 7 Citrus blue mold control effect After thoroughly washing citrus fruit (variety: Unshu) with water and air drying,
An emulsion of the compound of the present invention or a control commercially available drug was diluted with water and immersed for 1 minute in a drug solution to a predetermined concentration.

After air-drying, the drug-resistant or susceptible tangerine blue fungus (P
The conidia (Enicillium italicum) were suspended in water and inoculated by spraying onto the surface of the fruit.

After inoculation, the seeds were kept in a humid greenhouse for 14 days, and the degree of disease onset was investigated using the disease index of 0.1.2.3.4.5 as described below.

(Infection status) (Infection index) No lesions observed 0 -2-01 of fruit surface area
Lesions are observed in less than 1. Lesions are observed in less than 20-40% 2. 40-60 3 60-80 4? 8 (Lesions are observed in one or more areas) 5 The severity and control value were calculated in the same manner as in Test Example 1.

As a result, as shown in Table 8, 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 8 Note (1) Commercially available fungicide Benomyl Note (2) Thione mononate methyl Test Example 8 Phytotoxicity test on crops 150-capacity plastic pots were filled with sandy loam, and wheat (variety: Norin No. 61), Sow apples (variety: Kogyoku) and bean nuts (variety: Nichiba - semi-erect),
Grown in a greenhouse. A water-diluted solution of the test compound in the form of an emulsion or wettable powder 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 (signs) (symptoms) -No abnormality.

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

廿　　　　　　　　　　　　　　　　　　　　　　　 Abnormalities caused by chemical damage are observed.

: Obi The plant will wither and die due to chemical damage.

As a result, as is clear from Table 9, the compound of the present invention had no harmful effect on crops, and the commercially available herbicide with a chemical structure similar to that used as a control had a phytotoxic effect.

Table 9 Note (3) #Swep formulation example 1 Powder 2 parts of the compound of the present invention 5, 88 parts of clay and 10 parts of talc
By thoroughly pulverizing and mixing the two parts, a powder containing 2% of the main ingredient can be obtained.

Arrangement example 2 Wettable powder By thoroughly grinding and mixing 30 parts of the compound of the present invention 13, 45 parts of diatomaceous earth, 20 parts of white carbon, 3 parts of a wetting agent (sodium lauryl sulfate) and 2 parts of a dispersing agent (calcium lignin sulfonate), the main agent is obtained. A hydrating agent with a content of 30% is obtained.

Formulation Example 3 Wettable powder: 50 parts of Compound 14 of the present invention, 45 parts of diatomaceous earth, wet! By thoroughly grinding and mixing 2.5 parts of agent No. 11 (calcium alkylbenzenesulfonate) and 2.5 parts of a dispersant (calcium ligninsulfonate), a wettable powder having a base ingredient content of 50 g6 is obtained.

Formulation Example 4 Emulsion By mixing 10 parts of the compound 18 of the present invention, 80 parts of cyclohexanone, and 10 parts of an emulsifier (polyoxyethylene alkyl allyl ether), an emulsion with a base agent content of 10% is obtained.

Continuation of page 1 0 shots: Shigeo Yamamoto Sumitomo 4-2-1 Takashi, Takarazuka City Within Kagaku Kogyo Co., Ltd. 0 shots clear person Katsuzo Kamoshita Sumitomo 4-2-1 Takashi, Takarazuka City Within Kagaku Kogyo Co., Ltd. Procedural amendment (voluntary) June 16, 1981 Joined the Patent Office - Kazuo Wakasugi 1 Display of incident 1981 Patent Application No. 59598 λ Name of invention Aniline derivatives, their production methods and Agricultural and horticultural fungicide containing it as an active ingredient 3. Person making the amendment Relationship to the incident: Tokucho applicant Representative Takeshi Tsuchikata 4th generation... Address: 409-5-15 Kitahama, Higashi-ku, Osaka

Claims (1)

[Scope of Claims] (1) General formula [where x and y are the same or different, a halogen atom, a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a general formula]
It shows a group represented by CH20R2°-COOR2. Here, R2 represents a lower alkyl group. However, XY does not represent a hydrogen atom at the same time. K is the general formula -CH2
R3, -COR4, -5O□R, Te represents the group represented. Here, R3 represents a cyano group, a lower cyanoalkyl group, or a lower alkylthio group, R4 represents a lower alkyl group, a lower alkoxy group, or a lower alkylamino group; shows. 2 represents a group represented by the general formula W-R6. Here, W represents an oxygen atom or a sulfur atom, and R6 represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower haloalkyl group, or a lower alkoxyalkyl group 1. ] Aniline derivative represented by. (2) General formula [where x and y are the same or different, halogen atom, hydrogen atom, lower alkyl group, lower alkoxy group, or general formula
-CM2OR2゜Represents a group represented by COOR2. Here, 2 represents a lower alkyl group. However, XY does not represent a hydrogen atom at the same time. λ is the general formula -CH2R
It shows a group represented by 3,-COR,, -802R,. Here, R3 represents a cyano group, a lower cyanoalkyl group, or a lower alkylthio group, R4 represents a lower alkyl group, a lower alkoxy group, or a lower alkylamino group; shows. ] A compound represented by the general formula [wherein 2 represents a group represented by the general formula -WR]. Here, W represents an oxygen atom or a sulfur atom, and R6 represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower haloalkyl group, or a lower alkoxyalkyl group. [In the formula, x, y, z, and are as described above.] ] A method for producing an aniline derivative represented by (3) General formula [wherein, X and Y are the same or different, halogen atom, hydrogen atom, lower alkyl group, lower alkoxy group, or general formula
-CH2OR,. Indicates a group represented by COOR2. Here, R2 represents a lower alkyl group. However, xY does not simultaneously represent a hydrogen atom. Good □ has the general formula -CH2R3,COR,, -
80, represents a group represented by R. Here, R3 represents a cyano group, a lower cyanoalkyl group, or a lower alkylthio group, R4 represents a lower alkyl group, a lower alkoxy group, or a lower alkylamino group, and R6 represents a lower alkyl group, a lower haloalkyl group, or a lower alkylamino group. show. ] Phenyl isocyanate derivatives represented by the general formula [wherein 2 represents a group represented by the general formula -WR]. Here, W represents an oxygen atom or a sulfur atom, and R6 represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower haloalkyl group or a lower alkoxyalkyl group. [In the formula, x, y, z and □ are as described above. ] A method for producing an aniline derivative represented by (4) General formula [wherein X and Y are the same or different, a halogen atom, a hydrogen atom, a lower alkyl group, a lower alkoxy group, or the general formula -CH, OR,]. Indicates a group represented by COOR8. Here, R2 represents a lower alkyl group. However, xy does not represent a hydrogen atom at the same time. Chiku, general formula -CHR, -C:OR, 8
02R, shows the group represented by Table 28 4. Here, R represents a cyano group, a lower cyanoalkyl group, or a lower alkylthio group, - represents a lower alkyl group, a lower alkoxy group, or a lower alkylamino group, and R5 represents a lower alkyl group, a lower haloalkyl group, or a lower alkylamino group. shows. ] General formula obtained by reacting a compound represented by the following with phosgene [wherein, X, Y and Ni are as described above. ] A phenyl isocyanate derivative represented by the general formula [wherein 2 represents a group represented by the general formula -:WR]. Here, W represents an oxygen atom or a sulfur atom, and R6 represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group,
(lower) 10 alkyl group or lower alkoxyalkyl group. [In the formula, X, Y, Z and 1. is as described above. ] A method for producing an aniline derivative represented by [In the formula, X and Y are the same or different, a halogen atom, a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a general formula
-0H20R2゜GOOR, represents a group. Here, R2 represents a lower alkyl group. However, XY does not represent the same number ζ hydrogen atom. 2 represents a group represented by the general formula -W R6. Here, W represents an oxygen atom or a sulfur atom, and R6 represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower haloalkyl group, or a lower alkyl alkyl group. ] and a phenol derivative represented by the general formula RIRγ [wherein, □ represents a group represented by the general formula -CI(, R,, -COR4°-80, R5, where k is a cyano group, a lower A cyanoalkyl group, a lower alkylthio group, R4 represents a lower alkyl group, a lower alkoxy group, a lower alkylamino group, and the tag represents a lower alkyl group, a lower haloalkyl group, a lower alkylamino group. A method for producing an aniline derivative represented by the general formula [wherein x, y, z and 1□ are as described above], characterized by reacting the aniline derivative with a compound represented by the following. (6) General formula (wherein, Here, R8 represents a lower alkyl group. However, XY does not represent a hydrogen atom at the same time.] A 4-aminophenol derivative represented by δ [wherein 2 is the general formula -W-R, Indicates a group represented by, where W represents an oxygen atom or a sulfur atom, R6 is a lower alkyl group, lower alkenyl i, lower alkynyl i,
(lower) represents a lower alkyl group or a lower alkoxyalkyl group. [In the formula, X, Y and 2 are as described above. ] -802R5 represents a group. Here, R3 represents a cyano group, a lower cyanoalkyl group, or a lower alkylthio group, R4 represents a lower alkyl group, a lower alkoxy group, or a lower alkylamino group, and R6 represents a lower alkyl group, a lower haloalkyl group, or a lower γ-alkylamino group. shows. R7 is
Indicates a leaving group. [In the formula, x, y, z and symbols are as described above. ] A method for producing an aniline derivative represented by (7) General formula C In the formula, X and Y are the same or different, a halogen atom, a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a general formula
-CH2OR2°-GOOR2 represents a group. Here, R2 represents a lower alkyl group. However, xY does not simultaneously represent a hydrogen atom. ] A 4-hydroxyphenylisocyanate derivative represented by the general formula [wherein Z represents a group represented by the general formula -W-R6]. Here, W represents an oxygen atom or a sulfur atom, and R6 represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower haloalkyl group, or a lower alkoxyalkyl group. [In the formula, X, Y and 2 are as described above.] ] A phenol derivative represented by the general formula 1% [wherein R□ is the general formula -CH2R2s, -COR4゜-
80, represents a group represented by R. Here, RB represents a cyano group, a lower cyanoalkyl group, or a lower alkylthio group, R4 represents a lower alkyl group, a lower alkoxy group, or a lower alkylamino group; Indicates the group. ~ represents a leaving group. [In the formula, x, y, z and Ni are as described above.] ] A method for producing an Al derivative. (8) Represents a group represented by the general formula (wherein X and Y are the same or different), a hydrogen atom, a lower alkyl group, a lower alkoxy group, or the general formula -CH2OR2°GOOR.
Here, R2 represents a lower alkyl group. However, XY does not represent a hydrogen atom at the same time. General formula Y obtained by reacting a 4-aminophenol derivative represented by ] with phosgene [wherein, X and Y are as described above. ] and the 4-hydroxyphenylisocyanate derivative represented by the general formula [wherein 2 represents a group represented by the general formula -W-R6]. Here, W represents an oxygen atom or a sulfur atom, and the symbol represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower haloalkyl group, or a lower alkoxyalkyl group. [In the formula, X, Y and 2 are as described above. ] A phenol derivative represented by the general formula R1-Chikufu [wherein λ is the general formula -CH2R3, -COR4゜-3
Indicates a group represented by 02R6. Here, R3 represents a cyano group, a lower cyanoalkyl group, a lower alkylthio group,
R4 represents a lower alkyl group, a lower alkoxy group, or a lower alkylamino group, and R6 represents a lower alkyl group, a lower haloalkyl group, or a lower alkylamino group. R7 represents a leaving group. [In the formula, X, Y, Z and Ni are as described above.] ] A method for producing an aniline derivative represented by (9) General formula [wherein, X and Y are the same or different, a halogen atom, a hydrogen atom, a lower alkyl group, a -alkoxy group, or a general formula -
CH20R,. Indicates a group represented by COOR. Here, R2 represents a lower alkyl group. However, XY does not represent a hydrogen atom at the same time. East, is the general formula -CH2R,, -〇OR4, -80□R
It is represented by 6 and indicates a ◆ group. Here 1. represents a cyano group, a lower cyanoalkyl group, or a lower alkylthio group; R4 represents a lower alkyl group, a lower alkoxy group, or a lower alkylamino group; K represents a lower alkyl group, a lower haloalkyl group, or a lower alkylamino group; Z shown is general formula 1: W-
Indicates a group represented by R. Here, W represents an oxygen atom or a sulfur atom, and R6 represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower haloalkyl group, or a lower alkoxyalkyl group. ] An agricultural and horticultural fungicide characterized by containing an aniline derivative represented by the following as an active ingredient.