JPH0655707B2 - N- (2-chloro-4-nitrophenyl) -benzenesulfonamide derivative and agricultural fungicide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention provides compounds represented by general formula (I) (In the formula, X, Y and Z each represent hydrogen, a chlorine atom or a methyl group, and A represents a hydrogen or chlorine atom) N- (2-chloro-4-nitrophenyl)
-A benzenesulfonamide derivative and an agricultural fungicide containing the same.

The compound of the present invention is agriculturally useful as a soil fungicide.

[Conventional technology]

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 growing area of vegetables has become a housing complex, and the tendency of continuous production of commercial crops has become stronger, and the control of soil diseases has become more and more important. However, the control of soil diseases has been extremely difficult from the beginning, and the damage tends to increase at present. For example, PCBN (pentachloronitrobenzene) is used as a silver bullet for root-knot disease of cruciferous vegetables, but its application amount is so high that it is called fertilizer-like. 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. By the way, environmental pollution of agriculture has become a social problem, and there is no reason to leave such a large amount of drug abandoned, and there is a great demand for an effective drug with a lower dose to replace it. strong. Other soil diseases, such as potato scab, potato powdery scab, sugar beet root rot, wheat stripe dwarf, Japanese radish crack browning, turnip root constriction, pea root rot, big vein disease of lettuce, etc. On the other hand, it is difficult to completely control diseases with almost all drugs.

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 field of agriculture, insecticides as well as herbicides and fungicides have been studied. For example, as herbicides, Japanese Patent Publication No. 39-2957, 40-19
No. 199, and as a fungicide, Japanese Patent Publication Sho 4
4-9304, 45-6836, 46-6797, 47-15119, and JP-A-57-31655, 58-118558, 58-219159 and the like. Further, as an insecticide, U.S. Pat.
955 (1962) is given.

Japanese Patent Publication Nos. 58-118558 and 58-2191
No. 59 discloses a control action against root-knot disease of cruciferous vegetables, but its sulfonamide derivative is limited to a 3-nitrobenzenesulfonamide derivative. Moreover, none of the other prior arts described or suggested application 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 has a high activity, a low dose, and a less effective environmental impact fungicidal compound and fungicides for soil diseases. It is an object to provide a 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 known literatures, and having highly active soil bactericidal properties.

That is, the compound according to the present invention has the general formula (I) (In the formula, X, Y and Z each represent hydrogen, a chlorine atom or a methyl group, and A represents a hydrogen or chlorine atom.) N- (2-chloro-4-nitrophenyl)-
It is a benzenesulfonamide derivative.

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, the sulfonamide derivatives are thought to have different physiological activities due to the difference in their structures, and the compounds of the present invention have a broad spectrum and high activity against soil diseases. It cannot be predicted from the above-mentioned prior art that it has a controlling effect.

The compound (I) of the present invention is synthesized by the reaction represented by the following formula.

(In the formula, X, Y and Z each represent hydrogen, a chlorine atom or a methyl group, and A represents a hydrogen or chlorine atom.) The base used in the reaction is pyridine, triethylamine, trimethylamine, sodium hydride, sodium metal, etc. However, pyridine, sodium hydride and sodium metal are more suitable.

As the reaction solvent, toluene, xylene, chlorobenzene, dichlorobenzene, dimethylformamide, 1,3-
Dimethyl-2-imidazolidinone and the like can be used, but those having a boiling point of 110 ° C. or higher are 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 to 15 ° C.
Time 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, powdery scab of potatoes, radish radish of sugar beet, stripe dwarf of wheat, wilting of taisai, root rot of taisai, crack browning of radish, turnip of turnip. Root constriction,
It exhibits an excellent control effect against root rot of pea, big vein disease of lettuce, various bacterial wilt diseases. It also shows antibacterial activity against Gram-positive bacteria against 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 it is generally effective in the range of 0.2 to 40 kg per hectare, preferably 0.5 to 20 kg per hectare.

The compound of the present invention may be used as the raw material as it is, but usually, a carrier and, if necessary, other auxiliary agents are added and mixed to prepare a formulation form such as powder, wettable powder, granule, flowable agent and the like. To use. As the carrier, clays, talc, bentonite, calcium carbonate, diatomaceous earth, zeolite, inorganic substances such as silicic acid anhydride, wheat flour, soybean flour, starch, vegetable cellulose such as crystalline cellulose, petroleum resin,
Examples thereof include polymer compounds such as polyvinyl chloride and polyalkylene glycol, urea, waxes and the like. 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.

As auxiliary agents used for the purposes of wetting, dispersion, spreading, component stabilization, physical property stabilization, rust prevention, etc., various surfactants and gelatin, albumin, sodium alginate, methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, xanthan gum Polymer compounds such as and other auxiliary agents. Further, in the case of a flowable agent, an industrial bactericidal agent is optionally added for the purpose of antibacterial and antifungal.

As the surfactant, a nonionic substance such as one obtained by polymerizing ethylene oxide with an alkylphenol, a higher alcohol, an alkylnaphthol, a higher fatty acid, a fatty acid ester, a dialkylphosphate amine, or a polymer obtained by polymerizing ethylene oxide and propylene oxide is used. Surfactant,
Alkyl sulphates such as sodium lauryl sulphate, alkyl sulphonates such as sodium 2-ethylhexene sulphonate, anionic surfactants such as aryl sulphonates such as sodium lignin sulphonate and sodium dodecylbenzene sulphonate and various Examples include cationic and zwitterionic surfactants.

Further, when using the compound of the present invention as a fungicide, at the same time, other pesticides such as insecticides, fungicides, acaricides, nematicides, antiviral agents, herbicides, plant regulators, attractants, etc.
Not only can it be used in combination with a soil conditioner such as lime or a fertilizing substance, but a mixed preparation with these is also possible.

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, dressing, coating), seed soaking, seedling root dressing, root soaking, etc. can do.

The active ingredient in various dosage forms is usually 0.1 to 10% by weight for powders, 20 to 90% by weight for wettable powders, and 0.1 to 1 for granules.
0% by weight, and 20 to 90% by weight for a flowable agent is desirable.

〔Example〕

Next, the synthetic method of the compound of the present invention will be specifically described with reference to synthetic examples.

Synthesis Example 1 N- (2-chloro-4-nitrophenyl)-
2,5-Dimethylbenzenesulfonamide (Compound-4)
Synthesis of ortho-dichlorobenzene 200m in 400m flask
, Pyridine 1.6 g (0.02 mol) and 2-chloro-4-
1.7 g (0.01 mol) of nitroaniline was added, and 2.05 g (0.01 mol) of 2,5-dimethylbenzenesulfochloride was added to this mixture while stirring, at room temperature for 10 minutes. Then, the mixture was heated and refluxed ( 175-180 ° C) 10
The reaction was completed after stirring the time. After cooling to room temperature, the reaction solution was thoroughly washed with dilute hydrochloric acid and then with water, dehydrated with anhydrous sodium sulfate, and orthodichlorobenzene was distilled off under reduced pressure.
The target compound-4 was isolated from the residue by silica gel column chromatography (developing solution: benzene / ethyl acetate = 4/1).

mp125-127 ° C., yield: 1.4 g, yield: 41.2% Synthesis Example 2 Synthesis of N- (2,6-dichloro-4-nitrophenyl) -benzenesulfonamide (Compound-9) 1,3 in a 200 m flask. -Dimethyl-2-imidazolidinone 100m, 2,6-dichloro-4-nitroaniline
4.1 g (0.02 mol) was charged, and 1 g (0.0025 mol) of 60% sodium hydride was gradually added to this mixture at room temperature while stirring. The mixture was stirred for 1 hour as it was, then 3.5 g (0.02 mol) of benzenesulfochloride was gradually added, and a stirring reaction was carried out at 120 ° C. for 6 hours. After cooling, the reaction solution was poured into 200 m of cold water and left for a while.
The precipitated oily substance was extracted with 200 m of ethyl acetate, washed with dilute hydrochloric acid and then with water, and dehydrated with anhydrous sodium sulfate.
The solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography (developing solution: benzene / ethyl acetate =
The target compound 9 was isolated by 5/1).

mp156-157 ° C., yield: 2.8 g, yield: 40% Other compounds can also be synthesized according to either of the above Synthesis Examples 1 and 2.

Table 1 below shows typical examples and physical properties of the compound (I) of the present invention.

Next, formulation examples of the bactericide containing the compound (I) of the present invention as an active ingredient are shown, but the kind and mixing ratio of the additive are not limited to these.

Formulation Example 1 Dust 3 parts by weight of compound (2), 10 parts by weight of Carplex # 80 (white carbon manufactured by Shionogi & Co., Ltd.), clay 87
Parts by weight were mixed and pulverized to obtain a powder containing 3% by weight of the compound (2) as an active ingredient.

Formulation Example 2 Dust powder 0.5 parts by weight of compound (5), 49.5 parts by weight of calcium carbonate and 50 parts by weight of clay are mixed and pulverized to obtain compound (5) as an active ingredient.
A powder containing 0.5% by weight of was obtained.

Formulation Example 3 Dust agent 1 part by weight of compound (6), 5 parts by weight of Adeka Estor EX-1303 (manufactured by Asahi Denka Co., Ltd.), 44 parts by weight of calcium carbonate, and 50 parts by weight of clay were mixed and pulverized to obtain a compound as an active ingredient.
A powder containing 1% by weight of (6) was obtained.

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

Formulation Example 5 Wettable powder 80 parts by weight of Compound (1), 5 parts by weight of Carplex # 80 (Shionogi Pharmaceutical Co., Ltd., white carbon), 3 parts by weight of Emar 10 (Kao Corporation, surfactant) , Clay 1
2 parts by weight are uniformly mixed and pulverized to obtain a compound as an active ingredient.
A wettable powder containing 80% by weight of (1) was obtained.

Formulation Example 6 Granules 10 parts by weight of compound (4), 2 parts by weight of sodium dodecylbenzene sulfonate, 1 part by weight of sodium lignin sulfonate, 25 parts by weight of talc, 62 parts by weight of bentonite are uniformly mixed, extruded after hydrolysis and kneading. Granulate using a granulator and dry, then 10% by weight of compound (4) as an active ingredient.
A granule containing it was obtained.

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

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

Formulation example 9 Granules mixed with fertilizer 92 parts by weight of granular chemical fertilizer and ADEKA Estol EX-1303
(Asahi Denka Co., Ltd.) 2 parts by weight are uniformly mixed, and 6 parts by weight of the compound (1) is added to and mixed with this to obtain the compound (1) as an active ingredient.
A mixed granule with a fertilizer containing 6% by weight was obtained.

Formulation Example 10 Flowable agent 40 parts by weight of compound (10), 9 parts by weight of sodium ligninsulfonate, 1 part by weight of gum arabic, and 50 parts by weight of water are mixed and pulverized using a sand grinder to obtain compound (10) as an active ingredient. A flowable agent containing 40% by weight was obtained.

Test example 1 Chinese cabbage root-knot control test (Plasmodio phora brassica)
A predetermined amount of the dust preparation prepared according to Formulation Example 1 is added to 1 kg of soil contaminated with e), mixed well, and then filled in a clay pot having a diameter of 15 cm. Seed of Chinese cabbage (variety: Musou) 2
0 seeds were sown. This was grown in a greenhouse, and 6 weeks after sowing, the presence or absence of root disease was investigated. The control effect was expressed by obtaining the control rate from the following formula. The results are shown in Table-2.

Control rate (%) = Number of healthy strains / Number of surveyed strains × 100 Test Example 2 Komatsuna seedling wilt control test by Apharomyces raphari To 1 kg of sterilized soil, a predetermined amount of the dust preparation prepared according to the method of Formulation Example 2 was added, and well mixed with the whole amount of soil, and then filled in a ware pot with a diameter of 15 cm, 20 seeds of Komatsuna (variety: New Late-season Komatsuna) were sown. Prepared in advance 5 days after seeding
A zoospore suspension of Aphanomyces raphari (50 per field, 150 times) was irrigated with 50 m of soil per pot and inoculated. This was further grown in a greenhouse for 30 days, and the presence or absence of disease was observed and evaluated for each strain.

The control effect was expressed by the control rate as in Test Example 1. The test was done in 3 replicates.

The results are shown in Table 3 as an average value of 3 replicates.

Test Example 3 Pea root rot control test A predetermined amount of the dust preparation prepared according to Formulation Example 3 was added to 1 kg of soil contaminated with the pea root rot fungus Aphanomyces euteiches, and well mixed with the total amount of the soil, and this was prepared to have a diameter of 15 cm. Ten pea seeds were sown in a biscuit pot. This was grown in a greenhouse, the strain was taken out 30 days after seeding, and the degree of disease was observed and evaluated. The control effect is 4 from 0 to 3
It was expressed by the stepwise method, and this was expressed as the disease degree by the following formula. The test was performed in 3 replicates.

The results are shown in Table 4 as an average value.

Disease severity index 0: No disease 1: Low browning at the surface area 2: High 〃 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 the method of Formulation Example 2 was added to 1 kg of sterilized soil, mixed well, and then filled in a clay pot with a diameter of 15 cm, and sugar beet (variety: Monohill). 20 seeds were sown. The sugar beet bacterial wilt Ap prepared in advance after 3 days
A zoospore suspension of hanomyces cochilioides (50 cells / field of view, 150 times) was inoculated into each pot at 50 m. This was grown in a greenhouse, and on the 10th day after inoculation, the growth state of the seedlings was observed and evaluated, and 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 with soil to form a contaminated soil. This soil 8
A predetermined amount of the dust preparation prepared according to the method of Formulation Example 2 was added to kg, thoroughly mixed, and then 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. The survey carried out an observational evaluation of 5 stages of "0" to "4" for each tuber of about 20 g or more,
The disease severity was calculated from the following formula, and the control effect was tested.

The results are shown in Table-6.

Disease severity index 0: No lesions 1: 1 to 3 areas of lesions or lesions 3% or less 2: 4 to 10〃〃 4 to 13% 3：11 to 20〃〃 14 to 25% 4: 21 or more 〃 〃 26% or more Test Example 6 Potato Scab Disease Control Test (Seed Potato Coat Treatment) Seed potatoes infected with scab disease have at least 1 lesion site.
1 g of seed potatoes was coated with 100 g of the powder prepared according to the method of Formulation Example 1 after cutting so as to contain the above ingredients. This seed potato was planted in a 1 / 2.000 ares resin pot filled with upland soil and grown outdoors. On the 8th day after planting, the tubers were dug up and the disease state was investigated. Examination method is Test Example 5
The results are shown in Table 7.

[Effect of the invention] As is clear from the results of the above-mentioned 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 have been regarded as problems as difficult control diseases. Although some of the agents are commercially available, the compound of the present invention is clearly superior to these and extremely useful as a soil fungicide.

In addition, the compound of the present invention has a sufficient controlling effect against soil diseases caused by fungi similar to the pathogenic bacteria of these various soil diseases-for example, soybean root disease of sugar beet, and stripe wilt disease of wheat. Can be expected.

From the above description, the compound (I) of the present invention and agricultural fungicides containing them have a broader spectrum than conventionally known fungicides for soil diseases, and are highly active, and effective at a low dosage. It is clear that the present invention is an excellent soil disease fungicidal compound and a soil fungicidal composition having less environmental impact.

Continuation of front page Examiner Osamu Sato

Claims (2)

[Claims] 1. A general formula (I) At N- (2-chloro-4-nitrophenyl) -benzenesulfonamide derivative. 2. The general formula (I) At N- (2-chloro-4-nitrophenyl)-
An agricultural fungicide containing a benzenesulfonamide derivative.