JPH0627116B2 - N- (2-chloro-4-trifluoromethylphenyl) -3-trifluoromethylbenzenesulfonamide compound 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 and Y each represent a hydrogen atom or a chlorine atom.

However, at least one of X and Y represents a chlorine atom, and an N- (2-chloro-4-trifluoromethylphenyl) -3-trifluoromethylbenzenesulfonamide compound and a compound containing them. The present invention relates to a characteristic agricultural fungicide.

The compounds of the present invention and agricultural fungicides containing them are useful agriculturally as soil fungicides.

[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 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 at present. For example, for root-knot disease of cruciferous vegetables,
PCNB (pentachloronitrobenzene) is used as a silver bullet, but its application amount is so large that it is said to be similar to fertilizer. Furthermore, in fields where Brassicaceae vegetables are continuously cultivated, the standard application amount is already ineffective, and it is common sense to use a larger amount. By the way, environmental pollution of pesticides has become a social problem, and there is no reason that such drugs used in large quantities will be left unattended.Therefore, there is a need for effective drugs with lower dosages to replace them. Extremely strong. For other soil diseases such as potato scab, potato powder scab, sugar beet root rot, wheat stripe dwarf, radish crack browning, turnip neck, pea root rot, lettuce big bain disease, 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, examples of herbicides include Japanese Patent Publication No. 39-29571 and 40-191.
No. 99, and as a fungicide, Japanese Patent Publication No. Sho-44-9
Nos. 304, 45-6836, 46-6797, 47-15119, and JP-A-57-31655, 58-118558, 58-219159 and the like. Further, as an insecticide, US Patent 3,034,955 (196
2) can be given.

U.S. Pat. No. 3,034,955 (1962) discloses compounds of the formula:

The following compounds are mentioned as exemplary compounds.

3-Trifluoromethyl-4-chlorobenzenesulfonic acid-2 ', 4'-dichloro-5'-trifluoromethylanilide 3-trifluoromethyl-4-chlorobenzenesulfonic acid-3', 5'-bis- (trifluoro Methyl) -anilide 3-trifluoromethyl-4-chlorobenzenesulfonic acid-2'-trifluoromethyl-4'-chloroanilide 3-trifluoromethyl-4-chlorobenzenesulfonic acid-2 ', 5'-dichloro-4' -Trifluoromethylanilide 3-trifluoromethyl-4-chlorobenzenesulfonic acid-3'-trifluoromethyl-4'-chloroanilide The present compounds include compounds included in the above general formula, but the exemplified compounds are Not included and US Patent 3,034,
There is no description about the compound of the present invention in 955. Further, although the compound described in US Pat. No. 3,034,955 is disclosed to have insecticidal activity, nothing is mentioned about the action as a fungicide.

In addition, Japanese Patent Publication Nos. Sho 58-11858 and 58-21915.
Japanese Patent Publication No. 9 discloses the control action of a sulfonamide derivative against root-knot disease of cruciferous vegetables. However, these sulfonamide derivatives are limited to 3-nitrobenzenesulfonamide derivatives. None of the other above-mentioned prior arts describe or suggest 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 is highly active, effective at a low dose, and has less environmental impact, soil fungicidal compounds and 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 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 and Y each represent a hydrogen atom or a chlorine atom.

However, at least one of X and Y represents a chlorine atom) and is an N- (2-chloro-4-trifluoromethylphenyl) -3-trifluoromethylbenzenesulfonamide compound, which is a novel compound. .

The compounds of the present invention are distinct from the compounds disclosed in Japanese Patent Publication Nos. Sho 58-118558 and Sho 58-219159 in structure. As is clear from the above-mentioned prior art, the sulfonamide derivative exhibits various physiological activities such as herbicidal, bactericidal and insecticidal activities due to the slight difference in its structure, and the compound of the present invention is effective against soil diseases. Having a broad spectrum and highly active control action cannot be predicted at all from the prior art. Further, US Pat. No. 3,034,955 discloses a compound having a structure similar to that of the compound of the present invention. However, it is widely known that the substituents on the benzene ring greatly differ in physiological activity due to the difference in the number of substituents and the position of substitution even if the kind of the substituents is the same. The compound of the present invention has a structural feature in that it has a chlorine atom at the 2-position of the benzene nucleus of anilide and a trifluoromethyl group at the 4-position, and this point has excellent properties as a soil fungicide. Is produced. Therefore, from the insecticidal active substance disclosed in US Pat. No. 3,034,955, it is difficult to predict that the compound of the present invention has a high activity as a soil fungicide. In fact, as apparent from the test examples, the compounds disclosed in US Pat. No. 3,034,955 have no practical control effect as a fungicide.

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

(In the formula, each of X and Y represents a hydrogen atom or a chlorine atom. However, at least one of X and Y represents a chlorine atom.) The base used in the reaction is preferably pyridine, triethylamine, trimethylamine, etc. 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 reaction time vary depending on the solvent used,
The reaction temperature is preferably 110 to 180 ° C, and the reaction time is preferably 5 to 15 hours.

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 potato, radish radish of sugar beet, stripe dwarf of wheat, wilt of sugar beet, root rot of sugar beet, crack browning of radish, turnip of turnip Root constriction,
It shows an excellent control effect against root rot of pea, vine vein disease of lettuce, various seedling blight, etc. 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 amount varies depending on the type of target disease, various conditions such as soil conditions (pH, water, organic matter content, etc.) and weather conditions, but normally, Effectiveness is 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. Wetting, dispersion, spreading, component stabilization,
Stabilizing properties, auxiliary agents used for the purpose of rust prevention, various surfactants and gelatin, albumin, sodium alginate, methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polymer compounds such as xanthan gum and other auxiliary agents can give. 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, nonionic 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. 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.

When the compound of the present invention is used as a fungicide, at the same time, other agricultural chemicals such as insecticides, acaricides, nematicides, antiviral agents, herbicides, plant regulators, attractants, fungicides, 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 according to the generally customary application methods. That is, it is applied by 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. be able to.

The active ingredient in various dosage forms is usually 0.1-10% by weight for powders, 20-90% by weight for wettable powders, 0.1-10% by weight for granules, and 20-90% by weight for flowable agents.

〔Example〕

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

Synthesis Example 1 N- (2-chloro-4-trifluoromethylphenyl)
2-Chloro-5-trifluoromethylbenzenesulfonamide (Compound-1) A 400 ml flask was charged with 200 ml of ortho-dichlorobenzene, 1 ml of pyridine and 2.0 g (0.01 mol) of 2-chloro-4-trifluoromethylaniline, 2-chloro-5-trifluoromethylbenzene sulfochloride while stirring
2.8 g (0.01 mol) was added dropwise at room temperature over 5 minutes. Then, the mixture was heated and stirred under reflux (175 to 180 ° C.) for 8 hours. After the reaction solution was cooled to room temperature, it was thoroughly washed with diluted hydrochloric acid and then with water, dehydrated with anhydrous sodium sulfate, and orthodichlorobenzene was distilled off under reduced pressure. The target compound 1 was isolated from the residue by silica gel column chromatography (developing solution: benzene).

m.p. 122 to 123 ° C, yield 2.2 g, yield 50% Compound 2 was 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 kind and mixing ratio of the addition aid are not limited thereto.

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.), and 87 parts by weight of clay were mixed and ground, and 3% by weight of compound (2) as an active ingredient. A powder containing was obtained.

Formulation Example 2 Dust powder 0.5 parts by weight of compound (1), 49.5 parts by weight of calcium carbonate, and 50 parts by weight of clay are mixed and pulverized to obtain compound (1) as an active ingredient.
A powder containing 0.5% by weight was obtained.

Formulation Example 3 Dust agent 1 part by weight of compound (1), 5 parts by weight of Adeka Estol 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 prepare the compound (1 )
A powder containing 1% by weight of was obtained.

Formulation Example 4 Wettable powder 50 parts by weight of compound (2), 5 parts by weight of Solpol (surfactant manufactured by Toho Kagaku Co., Ltd.), 45 parts by weight of Radiolite (calcined diatomaceous earth manufactured by Showa Kagaku Co., Ltd.) are uniformly ground. By mixing, a wettable powder containing 50% by weight of compound (2) as an active ingredient was obtained.

Formulation Example 5 Wetting powder Compound (1) 80 parts by weight, Carplex # 80 (Shionogi Pharmaceutical Co., Ltd. white carbon) 5 parts by weight, Emar 10 (Kao Co., Ltd. surfactant) 3 parts by weight, clay 12 80 parts by weight of compound (1) as an active ingredient
A wettable powder containing it was obtained.

Production Example 6 Granules Compound (2) 10 parts by weight, sodium dodecylbenzene sulfonate 2 parts by weight, sodium lignin sulfonate 1 part by weight, talc 25 parts by weight, bentonite 62 parts by weight are uniformly mixed and after hydro-kneading, Granulation was performed using an extrusion granulator, and after drying, a granule containing 10% by weight of the compound (2) as an active ingredient 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 (1) was added and mixed to obtain a granule containing 3% by weight of compound (1) as an active ingredient. It was

Formulation Example 8 Granules mixed with fertilizer 97 parts by weight of granular chemical fertilizer and Dolores A (manufactured by Sankyo Co., Ltd.)
1 part by weight was uniformly mixed, and then 2 parts by weight of the compound (1) was added and mixed to obtain a mixed granule with a fertilizer containing 2% by weight of the compound (1) 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 (2), sodium lignin sulfonate 9
By weight, 1 part by weight of gum arabic and 50 parts by weight of water were mixed and pulverized using a sand grinder to obtain a flowable agent containing 40% by weight of the compound (2) as an active ingredient.

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 (Plasmodiophara brassica)
To 1 kg of soil contaminated in e), add a prescribed amount of the dust preparation prepared according to Preparation Example 1, mix well, and place in a clay pot with a diameter of 15 cm. 20 Chinese cabbage seeds (cultivar: Musou)
The 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.

Test Example 2 Control test for seedling wilt disease of Komatsuna by Aphanomyces raphani To 1 kg of sterilized soil, a predetermined amount of the dust preparation prepared according to Formulation Example 2 was added, mixed well with the whole amount of soil, and then placed in a biscuit pot with a diameter of 15 cm, Seeds of Komatsuna (variety: New Late Komatsuna) 20
The seeds were sown. 5 days after sowing, pre-prepared Aphano
zoospore suspension of myces raphani (50 per field, 150 times)
Was inoculated by irrigating 50 ml of soil per pot. This was further 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 expressed as a control rate by the following formula. 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 To 1 kg of soil contaminated with the 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 soil, and the diameter was 15 cm. 10 peas seeds were sown in a unglazed 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 was expressed by a 4-step method of the degree of disease on a scale of 0 to 3, and this was expressed as the degree of disease by the following formula.
The test was repeated 3 times.

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 To 1 kg of sterilized soil, a predetermined amount of powder prepared according to Formulation Example 2 was added, mixed well, and then placed in a clay pot with a diameter of 15 cm, and sugar beet (variety: Monohill) 20 seeds were sown. Apha, a bacterial wilt disease bacterium Apha prepared in advance 3 days later
zoospore suspension of nomyces cochilioides (50 per field,
150 times) was inoculated in 50 ml per pot. This is grown in a greenhouse, 10 days after inoculation, the growth condition of seedlings is observed and evaluated,
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 make a contaminated soil. This soil 8
Add a prescribed amount of powder prepared according to Formulation Example 2 to kg,
After mixing well, the pots made of resin of 1/2000 are were sown and potatoes (variety: male yak) were sown. This was grown outdoors, and tubers were dug 80 days after sowing, and the disease state was investigated. In the investigation, one tuber weighing about 20 g or more was observed and evaluated in five stages of "0" to "4", the disease degree was calculated by the following formula, and the control effect was tested. The results are shown in Table-6.

[Effect of the invention] As apparent from the above test examples, the compound of the present invention is root-knot disease of cruciferous vegetables, scab of potato, powdery scab, and soil diseases caused by various Aphanomyces bacteria, Shows excellent control effect. With respect to these soil diseases, which have been regarded as problems as difficult-to-control diseases, there is no excellent controlling agent and development is strongly desired. The compound of the present invention is clearly superior to some of the commercially available drugs and 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 than the conventionally known fungicides for soil diseases, and is highly active, and exhibits excellent effects on the environment because of its effect at a low dose. It is clearly a disease fungicide.

 ─────────────────────────────────────────────────── ─── Continuation of the front page Examiner Osamu Sato

Claims (2)

[Claims] 1. A general formula (I) (In the formula, X and Y each represent a hydrogen atom or a chlorine atom. However, at least one of X and Y represents a chlorine atom.) N- (2-chloro-4-trifluoromethylphenyl)- 3-Trifluoromethylbenzenesulfonamide compound. 2. The general formula (I) (In the formula, X and Y each represent a hydrogen atom or a chlorine atom. However, at least one of X and Y represents a chlorine atom.) N- (2-chloro-4-trifluoromethylphenyl)- An agricultural fungicide containing a 3-trifluoromethylbenzenesulfonamide compound.