JPS61271270A - N-(2-methyl-4-nitrophenyl)benzenesulfonamide compound and agricultural fungicide - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (X and Y are H, Cl or methyl; Z is H, Cl, cyano or trifluoromethyl). EXAMPLE:N-(2-methyl-4-nitrophenyl)benzenesulfonamide. USE:An agricultural fungicide. It exhibits excellent controlling effect especially against clubroot of vegetables of Cruciferae family, common scab of potato, and various soil blights caused by aphanomycete. It has high activity at a low dose and gives little environmental pollution. PREPARATION:The compound of formula I can be produced by reacting the compound of formula II with the compound of formula III in the presence of a base (e.g. pyridine) in a solvent (e.g. dichlorobenzene) at 110-180 deg.C for 5-15hr.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to agriculturally useful soil fungicides.

More specifically, the present invention relates to the general formula (1) (wherein X and Y each represent a hydrogen atom, a chlorine atom, or a methyl group, and 2 represents a hydrogen atom, a chlorine atom, a cyan group, or a trifluoromethyl group). The present invention relates to N-(2-methyl-4-nitrophenyl)benzenesulfonamide compounds represented by the following formulas and agricultural fungicides characterized by containing them.

[Prior art]

Crop diseases have traditionally been one of the major obstacles in crop cultivation. Among diseases, soil diseases caused by soil pathogenic bacteria are one of the most difficult problems.

Recently in Japan, vegetable cultivation areas have been turned into complexes, and there is a strong tendency for commercial crops to be continuously cultivated, making it increasingly important to control soil diseases. However, controlling soil diseases is extremely difficult to begin with. , the damage tends to increase more and more.

For example, for clubroot disease of cruciferous vegetables, PON
B (Pentachloronitrobenzene) f)”% efficacy.

However, the amount of application is so high that it is said to be equivalent to fertilizer (it is used).Furthermore, in fields where cruciferous vegetables are continuously cultivated, the standard application amount is already insufficiently effective, so a higher amount is used. It has become common sense to do so.On the other hand,
Environmental pollution caused by agricultural chemicals has become a social problem, and there is no reason for such chemicals that are used in large quantities to be left unattended, and there is an extremely strong demand for effective chemicals with lower dosages to replace them.

Other soil diseases such as potato scab, powdery scab, sugar beet scab, wheat striped wilt,
It is said that it is difficult to completely control cracks and degeneration of radish, turnip root disease, root rot of Japanese pea, big pain disease of lettuce, etc. with most drugs.

Many sulfonamide compounds have been synthesized since ancient times, and many studies have been conducted on their physiological activities. In the agricultural field, research is being conducted on not only herbicides and fungicides, but also insecticides. For example, as a herbicide, Japanese Patent Publication Publication No. 39-295
No. 71 and No. 40-19199, and as a disinfectant,
Japanese Patent Publication No. 1977-9304.45-6856
．． No. 46-6797.47-15119, Publication No. 1977
7-31655.58-118558.58-2191
Examples include No. 59. Further, examples of insecticides include US Pat. No. 3,034,955 (1962).

Japanese Patent Publication No. 58-118558 and 58
No. 219159 discloses the controlling effect of sulfonamide derivatives on clubroot disease of cruciferous vegetables. However, these sulfonamide compounds
- It is limited to nitrobenzenesulfonamide derivatives, and none of the other prior art mentioned above describes its application as a soil fungicide.

[Problem to be solved by the invention]

The present invention provides soil disease fungicidal compounds and soil disease fungicides that have a broader spectrum than conventional soil disease fungicides, are highly active, are effective at low dosages, and have less impact on the environment. An object of the present invention is to provide a sterilizing composition for use in the present invention.

[Means and effects for solving the problem] In order to solve the above problem, the present inventors focused on the fact that sulfonamide derivatives have various physiological activities, and as a result of intensive studies on sulfonamide derivatives, The present invention has been completed by discovering a compound that has a broad spectrum that could not be expected from known literature and has highly active soil bactericidal properties against diseases, especially soil diseases for which there are currently no excellent control agents. .

That is, the compound according to the present invention has the general formula (I)2' (wherein X and Y each represent a hydrogen atom, a chlorine atom, or a methyl group, and 2 represents a hydrogen atom, a chlorine atom, a cyano group, or a trifluoromethyl It is a new compound represented by N-(2-methyl-4-nitrophenyl)benzenesulfonamide compound.

The compound of the present invention is disclosed in Japanese Patent Publication No. 58-11855.
The structure is clearly different from the compounds disclosed in No. 8 and No. 58-219159. As is clear from the prior art described above, sulfonamide derivatives exhibit various different physiological activities due to their structural differences.
The fact that the compounds of the present invention have a broad spectrum and highly active control action against soil diseases cannot be predicted from the above-mentioned prior art.

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.) The base used in this reaction is pyridine, triethylamine, or trimethylamine. etc., but pyridine is the most suitable. As the reaction solvent, inert organic solvents such as toluene, xylene, chlorobenzene, dichlorobenzene and the like can be used, but those having a boiling point of 110° C. or higher are suitable.

The reaction temperature and reaction time vary depending on the solvent used, but the reaction temperature is 110-180°C and the reaction time is 5-180°C.
5 hours is preferable.

The compound of the present invention exhibits antibacterial or growth-inhibiting activity against various plant pathogenic bacteria and can be applied to a wide range of plant diseases, but is particularly effective against soil diseases of various crops for which there are currently no effective control agents. .

For example, clubroot disease of cruciferous vegetables, scab disease and powdery scab disease of potatoes, scab disease of sugar beet, striped wilt disease of wheat, damping-off and root rot disease of sugar beet, and cracking and deformation disease of radish. It shows excellent control effects against turnip root rot, root rot of Japanese pea, Big Bay disease of lettuce, various seedling damping-off diseases, etc. It also has antibacterial activity against bacteria, particularly against Durham-positive bacteria.

When using the compound of the present invention as a soil treatment agent, the amount of application depends on the type of target disease, various conditions such as soil conditions (P
Although it varies depending on [H1 moisture, organic matter content, etc.] and weather conditions, it is generally effective in the range of 200g to 40 to 9 per hectare, preferably 500g per hectare.
-20 to 9.

Although the compound of the present invention may be used as it is, it is usually mixed with a carrier and other adjuvants as necessary.
It is used in preparations such as powders, wettable powders, granules, flowables, etc. Examples of carriers include inorganic substances such as clays, talc, bentonite, calcium carbonate, diatomaceous earth, zeolite, and silicic anhydride; vegetable organic substances such as wheat flour, soy flour, starch, and crystalline cellulose; petroleum resins;
Examples include polymer compounds such as polyvinyl chloride and polyalkylene glycol, urea, and waxes.

Further, examples of the liquid carrier include various oils, organic solvents, water, and the like.

Furthermore, auxiliary agents required for formulation, such as wetting agents, dispersants, fixing agents, spreading agents, etc., may be used alone or in combination as appropriate. Wetting, dispersion, spreading, ingredient stabilization,
Auxiliary agents used for purposes such as rust prevention include various surfactants, gelatin, albumin, sodium alginate,
Examples include polymeric compounds such as methylcellulose, carboxymethylcellulose, polyvinyl alcohol, and xanthan gum, and other auxiliary agents. Examples of surfactants include nonionic interfaces such as alkylphenols, higher alcohols, alkylnaphthols, higher fatty acids, fatty acid esters, dialkyl phosphate amines, etc., with ethylene oxide polymerized, and ethylene oxide and propylene oxide polymerized. Active agents, anionic surfactants such as alkyl sulfates such as sodium lauryl sulfate, alkyl sulfonates such as sodium 2-ethylhexene sulfonate, aryl sulfonates such as sodium lignosulfonate, and sodium dodecylbenzenesulfonate. and various cationic and zwitterionic surfactants. In the case of a flowable agent, an industrial fungicide may be added in some cases for antibacterial and antifungal purposes.

When the compound of the present invention is used as a fungicide, other agricultural chemicals such as insecticides, fungicides, acaricides, nematicides, antiviral agents, herbicides, plant regulators, attractants, lime, etc. Not only can it be used in combination with soil conditioners or fertilizing substances, but also mixed formulations with these are also possible. The various formulations or spray preparations containing the compounds of the invention can be applied by customary application methods. That is, application by spraying (e.g. dusting, dusting, liquid spraying), soil surface application, soil mixing application, surface application (e.g. painting, dusting, coating), seed soaking, root dressing of seedlings, root soaking, etc. The active ingredient in various formulations is usually 0.1 to 10% by weight for powders and 20 to 10% for wettable powders.
It is preferably 90% by weight, 0.1 to 10% by weight for granules, and 20 to 90% by weight for flowables.

〔Example〕

Next, the method of synthesizing the compound (I) of the present invention will be explained in detail using a specific synthesis example, and Table 1 shows the physical property values of the compound of the present invention.

Synthesis Example I Synthesis of N-(2-methyl-4-nitrophenyl)benzenesulfonamide [Compound (1)] 4
Orundichlorobenzene 100 in a round bottom flask
ml, pyridine 5d and 2-methyl-4-nitroanili:/10.5 g (0.05 m01) and, while stirring at room temperature, benzenesulfonyl chloride 8.8. !
;I (0.05 rml) was added gradually. After sowing, the reaction mixture was heated and stirred under reflux (175 to 180" CJ for 8 hours to complete the reaction. The reaction solution was washed successively with dilute hydrochloric acid and water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by methanol recrystallization to obtain the desired compound (1
) was able to be obtained. m9. 162-164°C, yield 11 g, yield 84%. Other compounds were also synthesized by the above method.

Next, a formulation example of a fungicide containing the compound of the present invention as an active ingredient will be shown, but the type and mixing ratio of the additive auxiliary agent are not limited thereto.

Formulation Example 1 Powder Compound (2) 3 parts by weight, Carplex+80 [White Carbon manufactured by Shionogi Choyaku Co., Ltd.] 10 parts by weight, Clay 8
7 parts by weight were mixed and ground to obtain a powder containing 3% by weight of compound (2) as an active ingredient.

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 were mixed and ground, and compound (4) was added as an active ingredient.
A powder containing 3% by weight of 4) was obtained.

Formulation Example 6 Powder Compound (5) 5 parts by weight, azocanistol FiX-13
03 [manufactured by Asahi Denka Co., Ltd.] 5 parts by weight, calcium carbonate 40
Part by weight and 50 parts by weight of clay were mixed and pulverized to obtain an aquarium containing 5% by weight of compound (5) as an active ingredient.

Preparation Example 4 50 parts by weight of hydrating compound (7), Tsurupol [Toho Chemical Co., Ltd.
5 parts by weight of [Surfactant] and 45 parts by weight of Radiolite [Showa Kagaku Co., Ltd. Ura-baked kerosene earth] were uniformly ground and mixed.
An aquarium containing 50% by weight of compound (7) as an active ingredient was obtained.

Formulation Example 5 Wettable powder compound (10) 60 parts by weight, Carplex ≠ 80 [White Carbon manufactured by Shiono Gifuyaku Co., Ltd.] 10 parts by weight, Emarl 10 [Kao Co., Ltd. Fissure surfactant] 3 parts by weight, 27 parts by weight of clay were uniformly mixed and pulverized to obtain an aquarium containing 60% by weight of compound (10) as an active ingredient.

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
Parts by weight, 25 parts by weight of talc, and 62 parts by weight of bentonite were uniformly mixed, mixed with water, and then granulated using an extrusion granulator. After drying, 10% by weight of compound (9) was added as an active ingredient.
Granules containing the following were obtained.

Formulation Example 7 Granules 96 parts by weight of granular calcium carbonate and Azocanistol EX
1 part by weight of -1303 (manufactured by Asahi Denka Co., Ltd.) was evenly mixed, 3 parts by weight of the pulverized compound (3) was added and mixed,
Granules containing 5% by weight of compound (5) as an active ingredient were obtained.

Formulation Example 8 Mixed Granules with Fertilizer 97 parts by weight of granular chemical fertilizer and 1 part by weight of Toliless Man [manufactured by Sankyo Co., Ltd.] were uniformly mixed, and 2 parts by weight of compound (8) was added and mixed thereto, and as an active ingredient. A mixed granule with fertilizer containing 2% by weight of compound (8) was obtained.

Formulation Example 9 Granular mixture with fertilizer 92 parts by weight of granular chemical fertilizer and Azocanistol Ex-1
2 parts by weight of sox (manufactured by Kadenka Co., Ltd.) were mixed uniformly, 6 parts by weight of compound (9) was added and mixed thereto, and mixed granules with fertilizer containing 6% by weight of compound (9) as an active ingredient were prepared. Obtained.

Formulation Example 1070 Apple Agent Add 50 parts by weight of water to 40 parts by weight of Compound (7), 9 parts by weight of sodium ligninsulfonate, and 1 part by weight of gum arabic, mix and pulverize using a sand grinder to obtain Compound (7) as an active ingredient. ) was obtained.

Next, the soil disease control effects of the compounds of the present invention and agricultural fungicides containing them will be specifically explained using test examples.

Test Example 1 Chinese cabbage clubroot disease control test Cruciferous vegetable clubroot fungus (P la!gnodiop
A predetermined amount of the powder prepared according to Formulation Example 1 was added to soil 1 and 9 contaminated with P. horabrassicae, mixed, and then packed in a clay pot with a diameter of 15 cm. 20 seeds of Chinese cabbage (variety: Muso) were sown on this.The seeds were grown in a greenhouse, and the presence or absence of disease onset on the roots was investigated 6 weeks after sowing.The control effect was determined by calculating the control rate using the following formula. The results are shown in Table-2.

Table-2 Control Compound A: Pentachloronitrobenzene C City M1B
:N-(2-chloro-4-nitrophenyl-4-1f
Leu-3-nitrobenzenesulfonamide
N8558] 0WN-(3,4-dichlorophenylene/L+-3,4-dichlorobenzenesulfonamide C 4 +5 Test Example 2 Komatsuna seedling damping-off control test by Aphanomyces raphani Sterilization ±11C9 Prepared according to Formulation Example 2 After adding the specified amount of the powder and thoroughly mixing it with the total amount of soil,
Komatsuna in a clay pot (variety: new late-ripening Komatsuna)
20 seeds were sown. Five days after sowing, add 50 ml of Aphanomyces raphani zoospore suspension (50 per field, 150x) prepared in advance per pot.
The soil was irrigated and inoculated. This was grown in a greenhouse for 30 days, and each plant was observed and evaluated for the presence or absence of disease. The pesticidal effect was expressed as a pesticidal rate in the same manner as in Test Example 1. The results are shown in Table-3.

Table 3 Control compound D: N-(2-chloro-5-trifluoromethylphenyl)-4-chloro-3-trifluoromethylbenzenesulfonamide [US Patent 3034955.1
91521 Test Example 3 Aphanomyces eutei root rot disease control test Aphanomyces eutei
Add a predetermined amount of the powder prepared according to Formulation Example B to soil 1 and 9 contaminated with ches, mix well with the entire amount of soil,
Place this in a clay pot with a diameter of 15 cm and 10 Ento seeds.
The grains were sown. This is grown in a greenhouse, and the plants are pulled out on the 30th day after sowing, and the severity of the disease is indicated in 4 stages from O to O.
This was expressed as the disease severity using the formula below. The results are in the table-
4.

Disease severity index 0: No disease onset 1: Browning at the ground level Slight 2: High 3: Death or just before death Table-4 Control compound B: Hydroxyinxazal [commercially available product] Test example 4 Sugar beet damping-off control test sterilization ± After adding a predetermined amount of the powder prepared according to Formulation Example 2 to 1 kg and thoroughly mixing, 20 seeds of Tsume sugar beet (variety: Monohill) were sown in a clay pot with a diameter of 15 CTn. After 3 days, the powder was prepared in advance. Sugar beet damping-off fungus A
A suspension of phanomyces cochi l1oides (50 plants per field of view, 150x magnification) was inoculated at 50 seeds per pot.The plants were grown in a greenhouse, and 10 days after inoculation, the growth status of the seedlings was observed and evaluated. The control rate was calculated using the formula.The results are shown in Table 5.

Table 5 Test Example 5 Potato scab control test Potato scab fungi cultured in advance in an oatmeal liquid medium are mixed into soil to prepare contaminated soil. Formulation example 2 for this soil 8 to 9
A predetermined amount of the powder prepared according to the above was added, thoroughly mixed, and then packed into a 1/2.000 are resin pot and sown with potatoes (variety: Futoshishaku).The plants were grown outdoors for 80 days after sowing. Tubers were excavated and the disease state was investigated.Tubers weighing about 20g/l or more were observed and evaluated on a 5-grade scale from O to 4, and the disease severity was determined using the formula below to test the control effect.Table- Results are shown in 6. Disease severity index 0: No lesions 1: Area of 1 to 3 lesions or lesions 3 Takupoto 2:
4-10 pieces 4-13% 3:11-
20 cases 14-25% 4: 21 cases or more 26% or more Table 6 [Effects of the invention] As is clear from the above test examples, the compounds of the present invention are effective against clubroot disease of cruciferous vegetables, scab disease of potatoes, Shows excellent control effects against powdery scab and soil diseases caused by various Aphanomyces bacteria. There are no excellent control agents for any of these soil diseases, which are regarded as difficult to control diseases, and their development is strongly desired. The compounds of the present invention are clearly superior to some commercially available agents and are extremely useful as soil fungicides, thus meeting this need.

In addition, sufficient control effects can be expected against soil diseases caused by bacteria similar to the pathogens of these various soil diseases, such as sugar beet root disease and wheat striped wilt.

From the above explanation, the compound of the present invention has a broader spectrum and higher activity than conventional fungicides for soil diseases, and is effective at a low dose, making it an excellent soil fungicide with little impact on the environment. It is clear that

Claims (7)

[Claims] (1) General formula (I) ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, X and Y each represent a hydrogen atom, chlorine atom, or methyl group, and Z represents a hydrogen atom, a chlorine atom, or a cyano or trifluoromethyl group). (2) The compound according to claim 1, wherein in the general formula (I), both X and Z are hydrogen atoms. (3) The compound according to claim 1, wherein in the general formula (I), both X and Y are hydrogen atoms, and Z is a cyano group or a trifluoromethyl group. (4) In general formula (I), X is a methyl group,
2. The compound according to claim 1, wherein one of Y and Z is a hydrogen atom and the other is a methyl group. (5) In general formula (I), X is a chlorine atom,
2. The compound according to claim 1, wherein Y is a hydrogen atom and Z is a chlorine atom or a trifluoromethyl group. (6) In general formula (I), X is a hydrogen atom,
2. The compound according to claim 1, wherein Y is a chlorine atom and Z is a chlorine atom or a trifluoromethyl group. (7) General formula (I) ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, X and Y each represent a hydrogen atom, chlorine atom, or methyl group, and Z represents a hydrogen atom, a chlorine atom, or a cyano An agricultural fungicide characterized by containing an N-(2-methyl-4-nitrophenyl)benzenesulfonamide compound represented by the following formula: