JPH0655708B2 - Sulfonamide compounds and agricultural fungicides - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to agriculturally useful soil fungicides. More specifically, the general formula (I) (In the formula, A is a phenyl group, a 4-methylphenyl group, 2,
4-dimethylphenyl group, 2,5-dimethylphenyl group, 4-chlorophenyl group, 2,5-dichlorophenyl group, 3,4-dichlorophenyl group, 3-trifluoromethylphenyl group, 4-chloro-3-trifluoromethyl group It represents a phenyl group, a 2-chloro-5-trifluoromethylphenyl group, a 3-cyanophenyl group or a naphthyl group, Y represents a chlorine atom, a trifluoromethyl group or a cyano group, and Z represents a nitrogen atom or a methine group. . However, when Z is a methine group and Y is a cyano group, A excludes a phenyl group, a 4-methylphenyl group or a 2,5-dichlorophenyl group. ) And a fungicide for agriculture characterized by containing them.

[Conventional technology]

BACKGROUND ART Conventionally, crop diseases have been one of the major obstacles in crop cultivation. Among the diseases, soil diseases caused by soil pathogens are one of the most problematic problems. Recently, in Japan, vegetable cultivating medium has become a housing complex,
With the increasing tendency of continuous cropping of commercial crops, the control of soil diseases becomes 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,
PCNB (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 in which cruciferous vegetables are continuously grown, standard effects have already been insufficient, and it is common knowledge to use larger amounts. 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 doses to replace them. Other soil diseases such as potato scab, powdery scab, sugar beet radish, wheat stripe dwarf, Japanese radish fissure blight, 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 field of agrochemicals, not only herbicides and fungicides, but also insecticides have been studied. For example, as a herbicide, Japanese Patent Publication 39-29571
No. 40-19199, as the fungicide, Japanese Patent Publication No. 44-9304, 45-6836, 46-6797, 47-15
119, JP 57-31655, 58-118558, 58-2191.
No. 59 etc. can be given. Also, as an insecticide, US patent
No. 3034955 (1962) is given.

Japanese Patent Publication Nos. 58-11858 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 has a high activity, a low dose, and a lesser effect on the environment. An object is to provide a soil disease fungicidal compound and a soil disease fungicidal 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 literature, 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, A is a phenyl group, a 4-methylphenyl group, 2,
4-dimethylphenyl group, 2,5-dimethylphenyl group, 4-chlorophenyl group, 2,5-dichlorophenyl group, 3,4-dichlorophenyl group, 3-trifluoromethylphenyl group, 4-chloro-3-trifluoromethyl group It represents a phenyl group, a 2-chloro-5-trifluoromethylphenyl group, a 3-cyanophenyl group or a naphthyl group, Y represents a chlorine atom, a trifluoromethyl group or a cyano group, and Z represents a nitrogen atom or a methine group. Represent.
However, when Z is a methine group and Y is a cyano group, A excludes a phenyl group, a 4-methylphenyl group or a 2,5-dichlorophenyl group. ) Is a novel compound that is a sulfonamide 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, the sulfonamide derivatives exhibit various physiological activities due to the difference in their structures, and the compounds of the present invention have a broad spectrum and high activity control against soil diseases. It is impossible to predict that there is an effect from the above-mentioned prior art.

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

(In the formula, A is a phenyl group, a 4-methylphenyl group, 2,
4-dimethylphenyl group, 2,5-dimethylphenyl group, 4-chlorophenyl group, 2,5-dichlorophenyl group, 3,4-dichlorophenyl group, 3-trifluoromethylphenyl group, 4-chloro-3-trifluoromethyl group It represents a phenyl group, a 2-chloro-5-trifluoromethylphenyl group, a 3-cyanophenyl group or a naphthyl group, Y represents a chlorine atom, a trifluoromethyl group or a cyano group, and Z represents a nitrogen atom or a methine group. . However, when Z is a methine group and Y is a cyano group, A excludes a phenyl group, a 4-methylphenyl group or a 2,5-dichlorophenyl group. The base used in this reaction is preferably pyridine, triethylamine, trimethylamine, etc., but pyridine is most suitable.

As the reaction solvent, organic solvents such as toluene, xylene, chlorobenzene and dichlorobenzene can be used, but when pyridine is used as the base, pyridine can be used as the solvent.

Although the reaction temperature and the reaction time vary depending on the solvent used, the reaction temperature is preferably 80 to 150 ° C, and the reaction time is preferably 30 minutes to 4 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, potato scab, granular scab, sugar beet scab, wheat stripe dwarf, sugar beet wilt, root rot, radish cracking blight, 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 to 40 kg per hectare, preferably 500 g to 2 per hectare.
It is 0 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 formulation such as a powder, a wettable powder, a granule, and a flooyfable. 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, dispersing agents, fixing agents, spreading agents, etc., can be used alone or in combination as necessary. As an auxiliary agent used for the purpose of wetting, dispersion, spreading, component stabilization, rust prevention, etc., various surfactants and gelatin, albumin, soda such as algin,
Examples thereof include polymer compounds such as methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, xanthan gum, and other auxiliary agents. 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. Anionic surface active agents such as surfactants, 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 Agents and various cationic and zwitterionic surfactants. In the case of a flowable agent, an industrial bactericidal agent may be added depending on the case in order to prevent bactericide and mildew.

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 according to the generally customary application methods. That is, spraying (for example, dusting, dusting, liquid spraying), soil surface application, soil admixture application, surface application (for example, application, dressing, coating), seed dipping, seedling root dressing, root dipping, etc. can do. The active ingredient of various dosage forms is usually 0.1 to 10% by weight for powders, 20 to 90% by weight for wettable powders, 0.1 to 10% by weight for granules, and 20 to 90% by weight for flowable agents. .

[Examples] Next, the method for synthesizing the compound (I) of the present invention will be described in detail with reference to specific synthesis examples. Representative examples of the compound (I) of the present invention and the physical properties thereof are shown in Table 1.

Synthesis example 1. N- (5-cyanopyridin-2-yl)-
Synthesis of 3-Cyanobenzenesulfonamide (Compound-7) Pyridine 100 was placed in a 200 m four-neck glass flask.
9.5 g (0.08 mol) of m- and 6-aminonicotinonitrile were charged, and 14 g (0.07 mol) of 3-cyanobenzenesulfonyl chloride was gradually added while stirring at room temperature. After that, the mixture was stirred at 90 to 100 ° C. for 2 hours, and then pyridine was distilled off under reduced pressure. The residue was discharged into 100 m of a 5% dilute hydrochloric acid aqueous solution, and the precipitated target compound-7 was taken. Purification was performed by ethanol recrystallization. mp227
~ 229 ° C, Yield 15g, Yield 75.5%, IR spectrum ν
^KBr _max (cm ^-1 ): 3200 to 2960 (broad), 3080, 2960 to 2600
(broad), 2240, 1640, 1600, 1500, 1355, 1165, 114
Five. Elemental analysis value: (see Table 1) Synthesis Example 2. N- (4-trifluoromethylphenyl)-
Synthesis of benzenesulfonamide (Compound-29) 50m toluene in 100m 4-neck glass flask,
Charge 1.8 g (0.011 mol) of 4-aminobenzotrifluoride and 1.2 g (0.015 mol) of pyridine, and stir at room temperature with stirring benzenesulfone chloride 1.8 g (0.010 mol).
Was added, and the mixture was heated to reflux for 1 hour. After allowing to cool, the reaction solution was discharged into cold water, and extracted by shaking twice with 100 m ethyl acetate. The organic layer was dried, concentrated, and the residue was recrystallized from isopropyl ether to obtain the target compound-29. m.
p .: 98.5 to 100.5 ° C., yield: 2.4 g, yield: 78.4%, IR spectrum ν ^KBr _max (cm ⁻¹ ): 3260, 1620, 1520,
1470, 1330, 1160, 1120 Elemental analysis value: (see Table 1) Other compounds were also synthesized according to Synthesis Examples 1 and 2.

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 agent: 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 are mixed and pulverized to contain 3% by weight of compound (2) as an active ingredient. Got

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

Formulation example 3. Dust agent 5 parts by weight of compound (6), 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 (16) was obtained.

Formulation example 4. Wettable powder Compound (32) 50 parts by weight, Solpol (Toho Chemical Co., Ltd. surfactant) 5 parts by weight, Radiolite (Showa Chemical Co., Ltd.)
45 parts by weight of calcined diatomaceous earth) was uniformly pulverized and mixed to obtain a wettable powder containing 50% by weight of the compound (32) as an active ingredient.

Formulation example 5. Wettable powder 60 parts by weight of compound (23), 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 (23) as an active ingredient.
A wettable powder containing 60% by weight of was obtained.

Formulation example 6. Granules 10 parts by weight of compound (15), 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 and kneaded with water, followed by extrusion granulation. After granulating using a machine and drying, a granule containing 10% by weight of the compound (15) as an active ingredient was obtained.

Formulation Example 7. Granules 96 parts by weight of granular calcium carbonate and Adeka Estol EX
-1303 (Asahi Denka Co., Ltd.) 1 part by weight is uniformly mixed, and 3 parts by weight of a pulverized product of the compound (3) is added to and mixed with the mixture, 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 Dolores A (Sankyo Co., Ltd.)
1 part by weight) and 2 parts by weight of the compound (41) were added and mixed to obtain a mixed granule with a fertilizer containing 2% by weight of the compound (41) as an active ingredient.

Formulation Example 9. Granules mixed with fertilizer 92 parts by weight of granular chemical fertilizer and Adeka Estol EX-1
303 (manufactured by Asahi Denka Co., Ltd.) 2 parts by weight are uniformly mixed, and 6 parts by weight of the compound (9) is added to and mixed with this to prepare a mixed granule with a fertilizer containing 6% by weight of the compound (9) as an active ingredient. Obtained.

Formulation example 10. Flowable agent 40 parts by weight of compound (25), 9 parts by weight of sodium lignin sulfonate, 1 part by weight of gum arabic and 50 parts by weight of water are added and finely pulverized using a sand grinder to obtain 40 parts of compound (25) as an active ingredient. A flowable agent containing wt% was obtained.

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 root-knot control test (Plasmodiophora brassica)
1 kg of soil contaminated by e) Formulation example 1. After adding and mixing a predetermined amount of the dust preparation prepared according to 1., the mixture was placed in a clay pot with a diameter of 15 cm. 20 seeds of Chinese cabbage (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 is shown in Table 2 when the control rate was calculated by the following formula.

Test example 2. Test for controlling seedling wilt of komatsuna using Aphanomycos raphani. A predetermined amount of the dust preparation prepared according to 1. was added, mixed well with the total amount of soil, and then filled in a clay pot with a diameter of 15 cm, and 20 seeds of Komatsuna (variety: New Late-season Komatsuna) were sown. Prepared in advance 5 days after seeding
A zoospore suspension of Aphanomyces raphani (50 cells / field of view, 150 times) was irrigated with 50 m of soil per pot and inoculated. This is grown in a greenhouse for 30 days, and the presence or absence of disease is checked 1
Each strain was observed and evaluated. The control effect is shown in Test Example 1. Similarly to the above, the control rate was used. The results are shown in Table-3.

Test example 3. Pea root rot control test 1 mg of soil contaminated with pea root rot fungus Aphanomyces euteiches was used to prepare Formulation Example 3. A predetermined amount of the dust preparation prepared according to 1. was added and mixed well with the total amount of soil, and this was packed in a bisque-fired body having a diameter of 15 cm, and 10 peas seeds were sown. 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 Formulation example per 1 kg of sterilized soil 2. After adding a predetermined amount of the dust preparation prepared in accordance with 1. and mixing thoroughly, the mixture was placed in a clay pot with a diameter of 15 cm, and 20 seeds of sugar beet (variety: Monohill) were sown. 3 days later, the sugar beet wilt Ap that had been prepared in advance was used.
Suspension of hanomyces cochilioides (50/1 field of view, 1
50 times) was inoculated in 50 m per pot. This was grown in a greenhouse, and on the 10th day after the inoculation, the growth condition of the young plant 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 Mix contaminated soil with potato scab cultivated in oatmeal liquid medium in advance. This soil 8
Formulation example in kg 2. After adding a predetermined amount of the dust preparation prepared according to 1. and thoroughly mixing, the mixture was filled in a resin pot of 1/2000 are and seeded with potato (variety: male shak). This was grown outdoors, and tubers were dug 80 days after sowing, and the disease state was investigated. In the investigation, tubers weighing about 20 g / 1 or more were observed and evaluated in 5 grades of 0 to 4, the disease severity was determined by 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 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 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.

Further, a sufficient control effect can be expected against soil diseases caused by fungi similar to the pathogenic bacteria of these various soil diseases such as root-root disease of sugar beet and stripe-rot 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 front page Examiner Osamu Sato

Claims (7)

[Claims] 1. A general formula (I) (In the formula, A is a phenyl group, a 4-methylphenyl group, 2,
4-dimethylphenyl group, 2,5-dimethylphenyl group, 4-chlorophenyl group, 2,5-dichlorophenyl group, 3,4-dichlorophenyl group, 3-trifluoromethylphenyl group, 4-chloro-3-trifluoromethyl group It represents a phenyl group, a 2-chloro-5-trifluoromethylphenyl group, a 3-cyanophenyl group or a naphthyl group, Y represents a chlorine atom, a trifluoromethyl group or a cyano group, and Z represents a nitrogen atom or a methine group. Represent.
However, when Z is a methine group and Y is a cyano group, A excludes a phenyl group, a 4-methylphenyl group or a 2,5-dichlorophenyl group. ) A sulfonamide compound represented by 2. In the general formula (I), Z is a methine group, Y is a cyano group, A is a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,5-dichlorophenyl group. The compound according to claim 1, which is a 3,4-dichlorophenyl group, a 3-trifluoromethylphenyl group, a 3-cyanophenyl group or a naphthyl group. 3. In the general formula (I), Z is a methine group, Y is a trifluoromethyl group, A is a phenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, 2,5. -Dimethylphenyl group, 4-chlorophenyl group, 2,5-dichlorophenyl group, 3,4-dichlorophenyl group, 3-trifluoromethylphenyl group, 4-chloro-3-trifluoromethylphenyl group, 3-cyanophenyl group or Claim 1 which is a naphthyl group.
The compound according to the item. 4. In the general formula (I), Z is a nitrogen atom, Y is a cyano group, A is a phenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethyl. Phenyl group, 4-chlorophenyl group, 2,5-dichlorophenyl group, 3-trifluoromethylphenyl group, 2-chloro-5-trifluoromethylphenyl group,
The compound according to claim 1, which is a 3-cyanophenyl group or a naphthyl group. 5. In the general formula (I), Z is a nitrogen atom, Y is a trifluoromethyl group, A is a phenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, 2,5. -The compound according to claim 1, which is a dimethylphenyl group, a 2,5-dichlorophenyl group, a 3-cyanophenyl group or a naphthyl group. 6. A patent in which Z is a nitrogen atom, Y is a chlorine atom, and A is a phenyl group, a 3-trifluoromethylphenyl group, a 3-cyanophenyl group or a naphthyl group in the general formula (I). A compound according to claim 1. 7. General formula (I) (In the formula, A is a phenyl group, a 4-methylphenyl group, 2,
4-dimethylphenyl group, 2,5-dimethylphenyl group, 4-chlorophenyl group, 2,5-dichlorophenyl group, 3,4-dichlorophenyl group, 3-trifluoromethylphenyl group, 4-chloro-3-trifluoromethyl group It represents a phenyl group, a 2-chloro-5-trifluoromethylphenyl group, a 3-cyanophenyl group or a naphthyl group, Y represents a chlorine atom, a trifluoromethyl group or a cyano group, and Z represents a nitrogen atom or a methine group. Represent.
However, when Z is a methine group and Y is a cyano group, A excludes a phenyl group, a 4-methylphenyl group or a 2,5-dichlorophenyl group. ) A fungicide for agriculture, comprising one or more sulfonamide compounds represented by the formula (1).