JPH0655709B2 - N- (2-methyl-4-nitrophenyl) benzenesulfonamide compound and agricultural fungicide - Google Patents

Description

TECHNICAL FIELD The present invention relates to agriculturally useful soil fungicides.

More specifically, the present invention has the general formula (I) (In the formula, X and Y each represent a hydrogen atom, a chlorine atom or a methyl group, and Z represents a hydrogen atom, a chlorine atom, a cyano group or a trifluoromethyl group.) N- (2-methyl-4) -Nitrophenyl) benzenesulfonamide compound and an agricultural fungicide containing the same.

[Prior art]

BACKGROUND ART Conventionally, crop diseases have been one of the major obstacles to crop cultivation. Among the diseases, soil diseases caused by soil pathogens are one of the most difficult problems.
Recently, in Japan, the cultivation area of vegetables has become a housing complex, and the tendency to continuously grow commercial crops has become stronger, and the control of soil diseases has become more and more important. However, it is extremely difficult to control soil diseases originally, and the damage tends to increase more and more. For example, for root-knot disease of cruciferous vegetables, PC
NB (pentachloronitrobenzene) is used as a silver bullet, but its application amount is so large that it is said to be similar to fertilizer. In addition, in fields where cruciferous vegetables are continuously grown, the standard application amount is already ineffective, and it is common knowledge to use a larger amount. On the other hand, environmental pollution of pesticides has become a social problem, and there is no reason for such drugs used in large amounts to be left untreated, and there is a strong demand for effective drugs with lower dosages to replace them. . Other soil diseases such as potato scab, powdery scab, sugar beet radish, wheat stripe dwarf, Japanese radish fissure and morbidity, turnip root constriction, pea root rot, lettuce. It is said that it is almost impossible to completely control Bicbain's disease with a drug.

A large number of sulfonamide compounds have been synthesized for a long time, and many studies have been conducted on their physiological activity. In the agricultural field, not only herbicides and fungicides but also insecticides have been studied. For example, as a herbicide, Japanese Patent Publication No. 39-29571
No. 40-19199, and examples of insecticides include Japanese Patent Publication No. 44-9304, 45-6836, 46-6797, 47-15119.
No. 57-31655, 58-118558, 58-219159 and the like. Further, as an insecticide, US Pat.
No. 955 (1962) is given.

Japanese Patent Publications Nos. 58-118558 and 58-219159 disclose the controlling action of sulfonamide derivatives against clubroot disease of cruciferous vegetables. However, these sulfonamide-based compounds are limited to 3-nitrobenzenesulfonamide derivatives, and none of the other prior arts described above apply to soil fungicides.

[Problems to be Solved by the Invention]

The present invention has a broader spectrum than conventionally known fungicides for soil diseases, and is a highly active, low-dose, low-dose effective soil-bactericidal compound and for soil diseases. An object is to provide a bactericidal composition.

[Means and Actions for Solving the Problems]

The present inventors focused their attention on the fact that sulfonamide derivatives have various physiological activities in order to solve the above-mentioned problems, and as a result of diligent studies on sulfonamide derivatives, various plant diseases, in particular, there is no excellent control agent to date. The present invention has been completed by finding a compound having a broad spectrum against soil diseases, which is completely unpredictable from publicly known documents, and having a highly active soil bactericidal property.

That is, the compound according to the present invention has the general formula (I) (In the formula, X and Y each represent a hydrogen atom, a chlorine atom or a methyl group, and Z represents a hydrogen atom, a chlorine atom, a cyano group or a trifluoromethyl group. Provided that X and Z are simultaneously a hydrogen atom. N-, indicated by
(2-methyl-4-nitrophenyl) benzenesulfonamide compound.

The compounds of the present invention are distinct from the compounds disclosed in Japanese Patent Publication Nos. 58-118558 and 58-219159 in structure. As is clear from the above-mentioned prior art,
Sulfonamide derivatives exhibit various different physiological activities due to the difference in their structures, and that the compound of the present invention has a broad spectrum and highly active control action against soil diseases, from the above-mentioned prior art. It cannot be predicted at all.

The compound of the present invention is synthesized by the reaction shown by the following formula.

(In the formula, X and Y each represent a hydrogen atom, a chlorine atom or a methyl group, and Z represents a hydrogen atom, a chlorine atom, a cyano group or a trifluoromethyl group.)
And Z exclude hydrogen atoms at the same time.

Preferable chlorine used in this reaction is pyridine, triethylamine, trimethylamine and the like, but pyridine is most suitable. As the reaction solvent, an inert organic solvent such as toluene, xylene, chlorobenzene or dichlorobenzene can be used, but one having a boiling point of 110 ° C. or higher is suitable.
The reaction temperature and the reaction time vary depending on the solvent used, but the reaction temperature is 110 to 180 ° C., and the reaction time is 5-1.
5 hours is desirable.

INDUSTRIAL APPLICABILITY The compound of the present invention exhibits antibacterial activity or growth inhibitory activity against various plant pathogens, and can be applied to a wide range of plant diseases, but particularly shows excellent effects against soil diseases of various crops for which there is no effective control agent up to now. . For example, root-knot disease of cruciferous vegetables, potato scab, grain scab, sugar beet scab, wheat stripe dwarf, sugar beet wilt, root rot, radish cracking and alteration, It shows an excellent control effect against root-root disease of turnip, root rot of pea, big vein disease of lettuce, and various seedling blight. Further, it has antibacterial activity against bacteria, especially against Gram-positive bacteria.

When the compound of the present invention is used as a soil treatment agent, its application rate depends on the type of target disease, various conditions such as soil conditions (p
H, water content, organic matter content, etc.) and climatic conditions, but is generally effective within a range of 200 g-40 kg per hectare, preferably 500 g per hectare.
It is -20 kg.

The compound of the present invention may be used as it is, but usually, a carrier and, if necessary, other auxiliary agents are added and mixed,
It is used after being prepared into a dosage form such as powder, wettable powder, granule, and flowable agent. As the carrier, clays, talc, bentonite, calcium carbonate, diatomaceous earth, zeolite, inorganic substances such as silicic acid, wheat flour, soybean flour, starch, vegetable organic substances such as crystalline cellulose, petroleum resin, polyvinyl chloride, Examples thereof include polymer compounds such as polyalkylene glycol, urea, waxes and the like. Also,
Examples of the liquid carrier include various oils, organic solvents and water.

Further, auxiliary agents required for the formulation, such as wetting agents, dispersants, sticking agents, spreading agents, etc., can be appropriately used alone or in combination as necessary. Wetting, dispersion, spreading, component stabilization,
As an auxiliary agent used for the purpose of rust prevention, various surfactants, gelatin, albumin, sodium alginate,
Examples thereof include polymer compounds such as methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, xanthan gum, and other auxiliary agents. Nonionic interfaces such as those obtained by polymerizing ethylene oxide with alkylphenol, higher alcohol, alkylnaphthol, higher fatty acid, fatty acid ester, dialkylphosphate amine, etc., or those obtained by polymerizing ethylene oxide and propylene oxide as the surfactant. Anionic surfactants such as activators, alkyl sulphates such as sodium lauryl sulphate, alkyl sulphonates such as sodium 2-ethylhexene sulphonate, aryl sulphonates such as sodium lignin sulphonate and sodium dodecylbenzene sulphonate And various cationic and zwitterionic surfactants. Further, in the case of a flowable agent, an industrial bactericidal agent is optionally added for the purpose of antibacterial and antifungal.

When the compound of the present invention is used as a fungicide, at the same time, other pesticides such as insecticides, fungicides, acaricides, nematicides, antiviral agents, herbicides, plant regulators, attractants, etc. and lime etc. Not only can it be used in combination with the soil conditioner or fertilizer, but also a mixed preparation with these. The various formulations or spray preparations containing the compounds of the invention can be applied by the generally customary application methods.
That is, spraying (for example, dusting, powdering, liquid spraying), soil surface application, soil mixing application, surface application (for example, application,
It can be applied by dressing, coating), seed dipping, root dressing of seedlings, root dipping and the like. The active ingredient in various dosage forms is usually 0.1 to 10% by weight for powders and 20 for wettable powders.
˜90% by weight, granules 0.1 to 10% by weight, flowable agents 20 to 90% by weight are desirable.

〔Example〕

Next, the synthetic method of the compound (I) of the present invention will be described in detail with reference to specific synthesis examples, and Table 1 shows the physical properties of the compound of the present invention.

Synthesis example 1. Synthesis of N- (2-methyl-4-nitrophenyl) benzenesulfonamide [Compound (1)] Ortho-dichlorobenzene 100 in a 4-neck round bottom flask.
m, pyridine 5 m and 2-methyl-4-nitroaniline 10.5 g (0.05 mol) were charged, and benzenesulfonyl chloride 8.8 g (0.05 mol) was stirred with stirring at room temperature.
l) Added slowly. After that, heat and reflux (175-1
The reaction was completed by stirring at 80 ° C. for 8 hours. The reaction solution was washed successively with diluted hydrochloric acid and water, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by recrystallization from methanol to obtain the desired compound (I). mp.
162 to 164 ° C., yield 11 g, yield 84%. Other compounds were also synthesized according to the above method.

Next, formulation examples of the bactericide containing the compound of the present invention as an active ingredient will be shown, but the mixing ratio of the type of the addition aid is not limited to this.

Formulation Example 1 Powder 3 parts by weight of compound (2), 10 parts by weight of Carplex # 80 [Shionogi Pharmaceutical Co., Ltd. white carbon], and 87 parts by weight of clay are mixed and pulverized to obtain 3 parts of compound (2) as an active ingredient. % Powder was obtained.

Formulation Example 2 Powder 3 parts by weight of compound (4), 47 parts by weight of calcium carbonate, and 50 parts by weight of clay are mixed and pulverized to obtain compound (4) as an active ingredient.
A powder containing 3% by weight of was obtained.

Formulation Example 3 Granules 5 parts by weight of compound (5), 5 parts by weight of Adeka Estol EX-1303 [manufactured by Asahi Denka Co., Ltd.], 40 parts by weight of calcium carbonate,
50 parts by weight of clay was mixed and pulverized to obtain a compound as an active ingredient.
A wettable powder containing 5% by weight of (5) was obtained.

Formulation Example 4 Wettable powder 50 parts by weight of compound (7), 5 parts by weight of Solpol [surfactant manufactured by Toho Kagaku Co., Ltd.], Radiolite [Showa Kagaku Co., Ltd.]
45 parts by weight of calcined diatomaceous earth] were uniformly pulverized and mixed to obtain a wettable powder containing 50% by weight of the compound (7) as an active ingredient.

Formulation Example 5 Wettable powder 60 parts by weight of compound (10), 10 parts by weight of Carplex # 80 [white carbon manufactured by Shionogi & Co., Ltd.], 3 parts by weight of Emar 10 [surfactant manufactured by Kao Corporation], clay 27
Part by weight is uniformly mixed and pulverized to obtain the compound (10) as an active ingredient.
A wettable powder containing 60% by weight of was obtained.

Formulation Example 6 Granules 10 parts by weight of compound (9), 2 parts by weight of sodium dodecylbenzenesulfonate, 1 part by weight of sodium ligninsulfonate, 25 parts by weight of talc, and 62 parts by weight of bentonite are uniformly mixed, extruded after hydrolysis, and then extruded. After granulating using a granulator and drying, a granule containing 10% by weight of compound (9) as an active ingredient was obtained.

Formulation Example 7 Granules 96 parts by weight of granular calcium carbonate and ADEKA Estol EX
-1303 (manufactured by Asahi Denka Co., Ltd.) 1 part by weight is uniformly mixed, and 3 parts by weight of a pulverized compound (3) is added and mixed therein, and a granule containing 3% by weight of the compound (3) as an active ingredient. Got

Formulation Example 8 Mixed granules with fertilizer 97 parts by weight of granular chemical fertilizer and drires A [Sankyo Co., Ltd.]
Production] 1 part by weight was uniformly mixed, and 2 parts by weight of the compound (8) was added and mixed therein to obtain a mixed granule with a fertilizer containing 2% by weight of the compound (8) as an active ingredient.

Formulation Example 9 Mixed granules with fertilizer 92 parts by weight of granular chemical fertilizer and Adeka Estol EX-1
303 [manufactured by Asahi Densei Co., Ltd.] 2 parts by weight are uniformly mixed, and 6 parts by weight of the compound (9) is added thereto and mixed, and mixed granules with a fertilizer containing 6% by weight of the compound (9) as an active ingredient. Got

Formulation Example 10 Flowable agent 40 parts by weight of compound (7), 9 parts by weight of sodium ligninsulfonate and 1 part by weight of gum arabic were added with 50 parts by weight of water, and mixed and pulverized using a sand grinder to prepare compound (7) as an active ingredient. ) Was obtained as a flowable agent.

Next, the soil disease control effect of the compounds of the present invention and agricultural fungicides containing them will be specifically described with reference to test examples.

Test Example 1 Chinese cabbage clubroot control test (Plasmodiophora brassica)
A predetermined amount of the dust preparation prepared according to Formulation Example 1 was added to 1 kg of soil contaminated with e) and mixed, and then the mixture was placed in a clay pot with a diameter of 15 cm. 20 seeds of Chinese cabbage (variety: Muso) were sown on this. This was grown in a greenhouse, and 6 weeks after sowing, the presence or absence of root disease was investigated. For the control effect, the control rate was calculated from the following formula. The results are shown in Table-2.

Test Example 2 Komatsuna seedling wilt control test by Aphanomyces raphani After adding a predetermined amount of the dust preparation prepared according to Formulation Example 2 to 1 kg of sterilized soil and mixing well with the total amount of soil, the mixture was placed in a clay pot with a diameter of 15 cm and komatsuna ( Variety: New late-season komatsuna) seeds 2
0 seeds were sown. 5 days after sowing, pre-prepared Apha
zoospore suspension of nomyces raphani (50/1 field of view, 1
50 times) was irrigated with 50 m of soil per pot and inoculated. This was grown in a greenhouse for 30 days, and the presence or absence of disease was observed and evaluated one by one. The control effect was represented by the control rate as in Test Example 1. The results are shown in Table-3.

Test Example 3 Pea root rot control test To 1 kg of soil contaminated with pea root rot fungus Aphanomyces euteiches, a predetermined amount of the dust preparation prepared according to Formulation Example 3 was added and well mixed with the total amount of the soil, and this was prepared to have a diameter of 15 cm. Ten peas seeds were sown in a biscuit pot. This was grown in a greenhouse and the strain was taken out 30 days after sowing, and the degree of disease was displayed in 4 stages of 0 to 3, and this was expressed as the disease degree by the following formula. The results are shown in Table-4.

Disease severity index 0: No disease 1: Browning of the edge area 2: Low 〃 High 3: Dead or just before death Test Example 4 Sugar beet wilt control test A predetermined amount of the dust preparation prepared according to Formulation Example 2 was added to 1 kg of sterilized soil and sufficiently mixed, and then the mixture was placed in a clay pot with a diameter of 15 cm and seeds of sugar beet (variety: Monohill) 20. The seeds were sown. Three
Aphanomyce, a sugar beet wilt fungus prepared in advance after a day
Suspension of s cochilioides (50 per field, 150x)
50m was inoculated per pot. This was grown in a greenhouse, and the growth condition of seedlings was observed and evaluated 10 days after inoculation,
The control rate was calculated by the following formula. The results are shown in Table-5.

Test Example 5 Potato Scab Disease Control Test Potato scab disease bacteria cultivated in an oatmeal liquid medium in advance are mixed into soil to form a contaminated soil. This soil 8
Add a prescribed amount of powder prepared according to Formulation Example 2 to kg,
After mixing thoroughly, the mixture was filled in a resin pot of 1 / 2.000 are and seeded with potato (variety: male shak). This was grown outdoors, and tubers were dug 80 days after sowing to investigate the disease state. In the survey, tubers weighing about 20 g / 1 or more were observed and evaluated in 5 grades of 0 to 4, and the degree of disease was determined by the following formula to test the control effect. The results are shown in Table-6.

Disease severity index 0: No lesions 1: 1 to 3 or less area of lesions or lesions 2: 4 to 10 〃 4 to 13% 3: 11 to 20 〃 14 to 25% 4: 21 or more 〃 26% or more [Effects of the Invention] As is clear from the above test examples, the compound of the present invention is excellent against root-knot disease of cruciferous vegetables, scab of potato, powdery scab, and soil diseases caused by various aphanomyces bacteria. Shows the control effect. There is no excellent control agent for any of these soil diseases, which are considered to be difficult control diseases, and development is strongly desired. The compound of the present invention is obviously superior to some of the commercially available drugs, is extremely useful as a soil fungicide, and meets this need.

In addition, a sufficient control effect can be expected against soil diseases caused by bacteria close to the pathogens of these various soil diseases, such as root disease of sugar beet and stripe dwarf disease of wheat.

From the above description, the compound of the present invention has a broader spectrum and higher activity than conventionally known fungicides for soil diseases, and is an excellent soil fungicide with little effect on the environment because it exhibits an effect at a low dose. It is clear that

Claims (6)

[Claims] 1. A general formula (I) (In the formula, X and Y each represent a hydrogen atom, a chlorine atom or a methyl group, and Z represents a hydrogen atom, a chlorine atom, a cyano group or a trifluoromethyl group. Provided that X and Z are simultaneously a hydrogen atom. N-, indicated by
(2-Methyl-4-nitrophenyl) benzenesulfonamide compound. 2. The compound according to claim 1, wherein in the general formula (I), X and Y are both hydrogen atoms, and Z is a cyano group or a trifluoromethyl group. 3. In the general formula (I), X is a methyl group, one of Y and Z is a hydrogen atom, and the other is a methyl group. Compound. 4. The formula (I), wherein X is a chlorine atom, Y is a hydrogen atom, and Z is a chlorine atom or a trifluoromethyl group. Compound of. 5. In the general formula (I), X is a hydrogen atom, Y is a chlorine atom, and Z is a chlorine atom or a trifluoromethyl group. Compound of. 6. General formula (I) (In the formula, X and Y each represent a hydrogen atom, a chlorine atom or a methyl group, and Z represents a hydrogen atom, a chlorine atom, a cyano group or a trifluoromethyl group, provided that X and Z are simultaneously a hydrogen atom. N-, indicated by
An agricultural fungicide containing (2-methyl-4-nitrophenyl) benzenesulfonamide compound.