JPS6216465A - Benzamide derivative, production thereof and soil blight controlling agent - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [R is group of formula II (X is H or lower alkyl) or branched alkyl; Y is H, halogen, lower alkyl, lower alkoxy, nitro, alkoxycarbonyl or CF3; n is 1-5]. EXAMPLE:N-(2-methylbenzenesulfonyl)-3-(quinoline-2-yloxy)benzamide. USE:A solid-blight controlling agent. PREPARATION:The compound of formula I can be produced by reacting the compound of formula III or its reactive derivative with the sulfonamide derivative of formula IV in an inert solvent such as benzene, THF, DMF, etc., at the boiling temperature of the solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention represents general formula (1) or a lower alkyl group. ) or a branched alkyl group, Y represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, an alkoxycarbonyl group, or a trifluoromethyl group, and n is 1
Indicates an integer between ~5. The present invention relates to a novel benzamide derivative represented by the following formula, a method for producing the same, and a soil disease control agent containing the derivative as an active ingredient.

The compound of the present invention represented by the above general formula (1) is a novel compound that has not been described in any literature, and is highly effective against soil diseases such as clubroot that occurs in crucianaceae plants.

[Conventional technology]

Continuous cropping failure is one of the important problems in agricultural production, and most of the causes are caused by soil diseases. Conventionally, controlling soil diseases is extremely difficult due to the ecology of their occurrence, and the development of superior control agents is desired. For example, the occurrence of clubroot, which occurs in cruciferous plants and is one of the important soil diseases, has increased in recent years, causing great damage to the production of Chinese cabbages, cabbages, turnips, etc.

In addition, beet root disease is caused by a soil-dwelling fungus called Polymyxa bitterae, which is transmitted by the beet root yellow vein virus, and the area where it occurs is currently expanding and the damage is increasing. Potato scab also causes great damage to potato production.

However, although various chemical control methods are currently being used to control soil diseases, sufficient control effects have not been obtained.

In particular, various chemical control methods have been used to control clubroot disease that occurs in cruciferous plants, but current commercially available drugs (such as pentachlornitrobenzene, which has an effective acid of 90%) have not yielded good results. There is no situation. That is, a sufficient control effect cannot be obtained unless the commercially available drug is applied in large quantities, and on the other hand, if it is applied in large quantities, there may be problems with safety and environmental pollution. Although the compound of the present invention is a new compound, we have completed the present invention by discovering that it is highly effective against soil diseases, particularly clubroot disease that occurs in cruciferous plants.

[Aspects of the invention]

The compound of the present invention can be easily synthesized by the method shown below.

The blank space or lower alkyl group is shown below. ) or a branched alkyl group, Y represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, an alkoxycarbonyl group, or a trifluoromethyl group, and n is 1
Indicates an integer between ~5. ] That is, substituted benzoic acid (II) or its reactive derivative and benzenesulfonamide derivative (
The compound (1) of the present invention can be obtained by condensing I[[).

Here, the reactive derivatives of substituted benzoic acid (n) include acid halides, acid anhydrides, esters, etc.
Generally, acid chloride is used here, and in this case, it is preferable to carry out the reaction in the presence of a dehydrochlorination agent. Examples of this dehydrochlorination agent include hydroxides such as sodium hydroxide and potassium hydroxide; Examples include carbonates such as sodium hydrogen, sodium carbonate, and potassium carbonate, and amines such as triethylamine and pyridine. Acid chloride can be synthesized from free acid and thionyl chloride, phosgene, phosphorus oxychloride, etc. The condensation reaction is preferably carried out in a solvent inert to the reaction. Examples of inert solvents include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, ether solvents such as diethyl ether, tetrahydrofuran, and dioxane, and polar solvents such as ethyl acetate, dimethylformamide, and dimethylsulfonamide. , or a mixture of them can be used. On the other hand, the benzenesulfonamide derivative (■) is added to sodium hydroxide, potassium hydroxide or sodium hydride,
It is also possible to use potassium hydride to prepare the sodium salt or potassium salt of the benzenesulfonamide derivative in advance and use it in the condensation reaction.

Although the reaction temperature can be set between room temperature and the boiling point of the solvent used, it is most advantageous in terms of operation to set it at the boiling point of the solvent. Those skilled in the art can easily set appropriate reaction conditions.

One of the raw materials, quinolin-2-yloxybenzoic acid or a derivative thereof, is obtained by obtaining quinolin-2-yloxybenzoic acid or a derivative thereof using an appropriate 2-halogenoquinoline or a derivative thereof and an ester of hydroxybenzoic acid as a raw material. It can be obtained by hydrolysis.

The method for obtaining the compound of the present invention will be shown below in more detail through Examples, but the present invention is not limited to these Examples.

For disaster relief purposes N-(2-methylbenzenesulfonyl)-3
Synthesis of -(quinolin-2-yloxy)benzamide (compound number 24) Synthesis of (113-(quinolin-2-yloxy)benzoic acid) 32.7 g (0.2 mol) of 2-chloroquinoline and ethyl 3-hydroxybenzoate 33.2 g of ester (0,2-
55.3 g (0.4 mol) of N,N-dimethylformamide finely powdered potassium carbonate was added to
The reaction was carried out at 140°C for 6 hours. After cooling, 500m of water
The separated oil was poured into 200ml of methylene chloride.
Extracted with l. The methylene chloride layer was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. 2 to this
100ml of 0% sodium hydroxide aqueous solution and 1 part of ethanol
00 ml was added and refluxed for 1 hour. After the reaction is complete, 40% water
Add 0ml and neutralize with hydrochloric acid water (pH 3-4)
The obtained crystals were filtered and dried to obtain 3-(quinoline-2).
-yloxy)benzoin #42.4g was obtained.

Weight 80. θ% Melting point 165-167℃ (2) 3-(
Synthesis of quinolin-2-yloxy)benzoic acid chloride Next, 26.5 g (0.1 mol) of the 3-(quinolin-2-yloxy)benzoic acid obtained here was mixed with 1 mol of dioxane.
Dissolved in 50 ml of thionyl chloride (35.7 g).
3 mol) was added. To this was added 0.5 ml of N,N-dimethylformamide as a catalyst, and the mixture was refluxed for 3 hours.

After the reaction was completed, dioxane and excess thionyl chloride were distilled off under reduced pressure. 200 ml of methylene chloride was added to the residue, followed by saturated hydrogen carbonation, and the mixture was washed with 200 ml of an aqueous solution of 200 ml of methylene chloride, followed by water, and the methylene chloride layer was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 27.0 g of 3-(quinolin-2-yloxy)benzoic acid chloride. Yield 9
5.3% Melting point 117-120°C (31 Synthesis of N-(2-methylbenzenesulfonyl)-3-(quinolin-2-yloxy)benzamide 2-methylbenzenesulfonamide 3.42g (0,
0.88 g (0.02 mol) of 60% sodium hydride was dissolved in 100 ml of anhydrous tetrahydrofuran.
2 mol) was added and refluxed for 1 hour. Add this reaction solution to 1
The previously obtained 3-(quinoline-2-
yloxy)benzoic acid chloride 5.67 g (0,
02 mol) was added. After the addition was completed, the mixture was refluxed for 1 hour.

After cooling, the reaction solution was poured into 300 ml of water, and the separated oil was extracted with 100 ml of methylene chloride. The methylene chloride layer was washed with water and dried over anhydrous sodium sulfate, and then methylene chloride was distilled off under reduced pressure. The residue was recrystallized with a mixed solvent of 20 ml of ethanol and 60 ml of toluene to obtain 4.12 g of N-(2-methylbenzenesulfonyl)-3-(quinolin-2-yloxy)benzamide. Yield 49.3
% Melting point 189.0-190.5℃ Elemental analysis value 0
% H% N% calculated value 66.02 4.33
6.69 Actual value 65.85 4.38 6
．． 55m1 Synthesis of N-(5-chloro-2-methylbenzenesulfonyl')-3-(quinolin-2-yloxy)benzamide (compound 11h 37) 5-chloro-2-methylbenzenesulfonamide 1.4
5 g (7.05 mmol) and 3-(quinoline-2-
yloxy)benzoic acid chloride 2.00 g (7,
05 mmol) was dissolved in 20+ml of dioxane and 1.30 g (9.41 mmol) of potassium carbonate were added. After the addition was complete, the mixture was refluxed for 4 hours. After the reaction was completed, dioxane was distilled off under reduced pressure, 100 ml of water was added to the residue, and insoluble matter was filtered off. Neutralize the filtrate with dilute hydrochloric acid to make it acidic (pH 3 to 4).
) The crystals obtained were filtered and dried to obtain 2.62 g of the target product.
I got it. (Yield 82.1%, melting point 188-192°C)
Elemental analysis value 0% H% N% calculated value 61
．． 00 3.78 6.18 Actual value 60.83
3.85 6.31 prong ±1 N-(2,4,6
,-)ethylbenzenesulfonyl)-4-tert-butylbenzamide (compound No. 9) Put 0.42 g (0.0105 mol) of sodium hydride (oil-based 60χ) into a 50 ml fourth flask,
15 ml of tetrahydrofuran dried in a conventional manner was added. In this solution, 2, 4, 6. - 2.41 g (0,010 mol) of triethylbenzenesulfonamide was added little by little, and after the addition, the mixture was stirred for an additional 20 minutes. -) A sodium salt solution of ethylbenzenesulfonamide was prepared. In this solution, 1.97 g (0,
A solution of 15 ml of dry tetrahydrofuran containing 4-tert-butylbenzoyl chloride (010 mol) was added dropwise little by little while stirring under water cooling. After the dropwise addition was completed, the reaction solution was heated and the tetrahydrofuran was refluxed for 4 hours.
After heating and stirring for 10 hours to complete the reaction, the reaction solution was heated for 40 minutes.
It was poured into 0 ml of water, and hydrochloric acid was added to the aqueous solution to make it strongly acidic (pH 1 to 2). After saturated with table salt,
The aqueous solution was extracted three times with 100 ml of methylene chloride, and the methylene chloride layer was extracted with 100 ml of saturated saline twice.
Washed twice.

After drying over anhydrous magnesium sulfate, the methylene chloride layer was concentrated under reduced pressure, and n-hexane was added to the residue to solidify it. This solidified product was recrystallized from toluene, and the obtained crystals were filtered and dried to obtain 2.12 g of the desired N-(2,4,6,-)ethylbenzenesulfonyl)-4-tert-butylbenzamide. I got it. (Yield 52.9
χ, melting point 164-172℃) Elemental analysis value 0% H% N% calculated value 68
,79 7.80 3.49 Actual value 68.62
7.71 3.63 Great Rejection Earth N-(2,4,6,
Synthesis of -1-cyisopropylbenzenesulfonyl)-4-tert-butylbenzamide (compound Na 12) 8.50 g (0,
030 mol) of 2.4,6. -Triisopropylbenzene sulfo, diamide, 5.40 g (0.039 mol) of potassium carbonate and 70 ml of dioxane were charged. In this solution at room temperature 5.90 g (0,030 mol) of 4-tert-butylbenzoyl chloride
30 ml dioxane solution was added little by little with stirring. After the addition was completed, the reaction solution was heated and stirred for 6 hours while dioxane was refluxing. After cooling, insoluble matter was filtered off and washed with 30 ml of dioxane. The filtrate and washing liquid were combined and condensed under reduced pressure, and 200 ml of ethyl acetate was added to the residue. 100 ml of ice water was added to this ethyl acetate solution, and while stirring vigorously, hydrochloric acid was added until the pH of the aqueous layer became strongly acidic (pH 1 to 2).

After separating the ethyl acetate layer, it was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was recrystallized from a mixed solvent of toluene:ethanol=1:1. The obtained crystals are collected by filtration and dried to obtain the desired N-(2,4,6,-)
9.06 g of (isopropylbenzenesulfonyl)-4-tert-butylbenzamide were obtained. (Yield 68
．． 1χ, melting point 204-206℃) Elemental analysis value 0% H% N% calculated value 68
．． 79 7.80 3.49 Actual value 68.62
7.71 3.63ffi N-(5-chloro-
Synthesis of (2-methylbenzenesulfonyl)-4-tert-butylbenzamide (compound No. 13) 6.17 g (0,
0.30 mol) of 5-chloro-2-methylbenzenesulfodiamide, 5.40 g (0.039 mol) of potassium carbonate and 70 ml of dioxane. A solution of 5.90 g (0,030 mol) of 4-tert-butylbenzoyl chloride in 30 ml of dioxane was added little by little to this solution at room temperature while stirring. After addition,
The reaction solution was heated and stirred for 8' hours while dioxane was refluxing. After cooling, the reaction solution solidified. This reaction solution was suction filtered through a glass filter, and the filtration residue was washed with a small amount of dioxane, then dispersed in 1000 ml of water, and hydrochloric acid was added while stirring at room temperature to make it strongly acidic (pH 1-2). The obtained precipitate was collected by filtration, washed with water, and then dried. This was recrystallized from ethanol, and the obtained crystals were collected by filtration and dried to obtain the desired N-(5-chloro-2-methylbenzenesulfonyl)-4-tert-butylbenzamide, 8.46
I got g. (yield 77.1!, melting point 210-21
2℃) Elemental analysis value 0% H% N% calculated value
59.08 5.52 3.83 Actual value 58.
93 5.42 3.96 or below Margin Next, examples of the compounds included in the present invention are shown in Tables 1 and 2 below along with the compounds synthesized in the above examples, but the compounds of the present invention are limited only to these. It's not a thing.

Table 1 Table 1 (continued) Table 2 Table 2 (continued) ■ Table 2 (continued) In Table 1 and Table 2, Me is a methyl group, t is an ethyl group, and 1-Pr is a The isopropyl group and t-Bu represent an unshaly butyl group.

When the compound of the present invention is applied as a soil disease control agent, a suitable carrier is generally used, such as a solid carrier such as clay talc, bentonite, diatomaceous earth, or calcylar carbonate, or water, alcohol (methanol, ethanol, etc.), aromatic carrier, etc. Hydrocarbons (benzene, toluene, xylene, etc.), chlorinated hydrocarbons, ethers, ketones, esters (
(ethyl acetate, etc.), acid amides (dimethylformamide, etc.), and can be used in combination with liquid carriers such as emulsifiers, dispersants, suspending agents, penetrating agents, spreading agents, stabilizers, and adjuvants, if desired. It can be put to practical use in any desired dosage form, such as a liquid, emulsion, wettable powder, powder, or granule.

In the case of solid dosage forms (powders, granules, wettable powders, etc.), the content of the compound of the present invention is not particularly limited, but is preferably about 0.1 to 60% by weight, and ,
It is preferably about 0.5 to 30% by weight.

On the other hand, in the case of liquid dosage forms (emulsions, solutions), the content of the compound of the present invention is not particularly limited, but is preferably about 0.5 to 90% by weight, and more preferably 2 to 90% by weight.
About 80% by weight is preferable. One method for applying the preparation of the present invention to soil is to apply it directly to the soil and mix it with the soil in the case of a powder or granule. Although the amount of the compound of the present invention to be treated is not particularly limited,
The amount per hectare is preferably about 0.1 to 200 kg, more preferably about 0.5 to 100 kg.

Another method is to dilute emulsions, solutions, and wettable powders with water to adjust the concentration of the compound of the present invention to a predetermined concentration, and then irrigate them into the soil. In this case, the concentration of the compound of the present invention is not particularly limited, but is preferably 1 to 2000 ppm, more preferably 50 to 11 ppm.
About 000 pp is preferable. The amount of the compound of the present invention to be treated is not particularly limited, but is preferably about 0.1 to 200 kg per hectare, more preferably about 0.5 to 100 kg.

Among the preparations of the present invention, powders are particularly preferred, and solid carriers for these powders are not particularly limited, but clay, talc, calcium carbonate, and diatomaceous earth are preferred, and one or more of these are preferred. Can be used. Furthermore, white carbon may be added as an auxiliary agent, if necessary. The preferred blending ratio is 1 to 20 of the compound of the present invention.
60 to 99 parts by weight of clay, talc, calcium carbonate or diatomaceous earth, and 0 to 20 parts by weight of white carbon (auxiliary agent) may be optionally blended.

The soil diseases that can be controlled in the present invention are not particularly limited, and include, for example, clubroot of cruciferous plants, scab of beets, scab of potatoes, and the like.

Next, examples of formulations of soil disease control agents containing the compounds of the present invention as active ingredients will be shown, but the soil disease control agents of the present invention are not limited to these. In addition, in the following formulation examples, "parts" mean parts by weight.

Inflammation Wettable powder Compound of the present invention ・−−−−・−−−−−1・
-25 parts Siegrite A...-----1--------...69 parts (kaolin clay:
Sieglite industrial music product name) Tsurupol 5039-・-
−−−−−m−・−−−−3 parts (Mixture of nonionic surfactant and anionic surfactant: Toho Chemical ■Product name) Carplex (anticaking agent) −・−3 (white carbon: Shionogi & Co., Ltd. trade name) or more is mixed and ground uniformly to make a wettable powder. When using the above hydrating agent, add 250~
Use after diluting 25,000 times.

Additional Examples - Emulsion Compound of the Invention ・−・−1−−−・・−・−−−
1--50 copies
−−−−−・−・−−−−1−−・25 parts dimethylformamide −・−・−・−20 parts Tsurpol 268
0 - - - - - - - - - 5 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical ■ trade name) - Mix the above uniformly to form an emulsion. do. When used, the above emulsion is diluted 500 to 50,000 times.

Formulation Example 3 Powder Compound of the Invention -・-・-・-5 parts clay
-------------- 95 parts or more are mixed uniformly to obtain a powder containing 5% of the active ingredient.

Next Ushimasu soil Powder Compound of the present invention --- 1 ---・・-・-・ 1
Part talc ・−・・・・−−1−−−−
- Mix 99 parts or more uniformly to obtain a powder containing 1% of the active ingredient.

Powder manufacturing method Compound of the present invention −1～−−−−−−−−−−−
・ 20 parts clay ・−・・−−−−−−
−−−・70 parts white carbon −・−・−・
-····························· Mix 10 parts or more uniformly to obtain a powder containing 20% of the active ingredient.

Takumi Kesume I Granules Compound of the present invention --------------
−−・ 5 parts bentonite −・−・・−−−−
−−−・−・ 25 parts talc ・−・・
・−・−・−−−1−・− After uniformly mixing and pulverizing 70 parts or more, add a small amount of water, stir and knead, granulate with an extrusion type granulator, and dry to form granules. Make it into a drug.

Next, the usefulness of the compound of the present invention as a soil disease control agent will be specifically explained in the following test examples.

Disappearance! 1. Test for controlling clubroot disease of cruciferous plants (emulsion treatment) Plastic pots with a diameter of 8C11 were filled with sterilized soil, and 3 seeds of Chinese cabbage (variety: Kinsho No. 2) were sown per pot. The emulsion shown in the formulation example was diluted to a predetermined concentration and 10 ml per pot was irrigated onto the surface of this pot. The next day after treatment, the clubroot disease fungus of cruciferous plants
The pot surface was inoculated with a suspension of dormant spores of the crucianaceae root gall fungus, obtained by homogenizing 1 g per pot of Chinese cabbage root galls formed by infection with S. ss 1cae). This was placed in a glass greenhouse, Chinese cabbage was allowed to grow, and the state of root growth was investigated 5 weeks after inoculation, and the control value was calculated using the following formula.

no + number of individuals in which root galls are not observed.

nl: Number of individuals with root galls growing only on the support plate.

n2: Number of individuals whose root galls are epiphytic on both the support plate and the taproot, but are not very enlarged.

n3: The number of individuals with root galls growing on both the support plate and the main root and significantly enlarged.

N: Total number of surveyed individuals.

PCNB permanent agent (75% active ingredient) was used as a control drug.

The results are shown in Table 3.

Table 3 Table 3 (continued) Table 3 (continued) PCNB 4! This is a commercially available soil disease control agent containing pentachlornitrobenzene and having the following structure.

Example 1 - Cruciferous plant clubroot control test (powder treatment) Powder 5 containing 180 g of sterilized soil and 5% of the compound of the present invention
0 mg was mixed well, packed into a/20000 bottles, and three Chinese cabbage seeds (variety Nikin-sho No. 2) were sown per pot. (Active ingredient treatment t: 5 kg/ha)
On the day after the treatment, 1 g per pot of Chinese cabbage root galls formed by infection with the cruciferous clubroot fungus (II. Inoculation was performed by irrigation of the solution onto the pot surface. This was placed in a glass greenhouse, Chinese cabbage was grown, and the state of root growth was investigated 5 weeks after inoculation, and the control value was calculated using the same method as in Test Example 1.

However, the control drug is PCNB powder (20% active ingredient)5
00 mg was used.

The results are shown in Table 4.

Table 4 Table 4 (continued)

Claims (3)

[Claims] (1) General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R is ▲There are mathematical formulas, chemical formulas, tables, etc.▼(However, X is a hydrogen atom or a lower alkyl group. ) or a branched alkyl group, Y represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, an alkoxycarbonyl group, or a trifluoromethyl group, and n is 1
Indicates an integer between ~5. ] A benzamide derivative represented by (2) General formula (II): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [In the formula, R is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, X is a hydrogen atom or a lower alkyl group. ) or a branched alkyl group. ] or its reactive derivative, and the general formula (III): ▲Mathematical formulas, chemical formulas, tables, etc.▼(III) [In the formula, Y is a hydrogen atom, a halogen atom, a lower alkyl group,
It represents a lower alkoxy group, a nitro group, an alkoxycarbonyl group, or a trifluoromethyl group, and n represents an integer of 1 to 5. ] General formula (I) characterized by reacting with a sulfonamide derivative represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R, Y and n are the same as above. ] A method for producing a benzamide derivative represented by (3) General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R is ▲There are mathematical formulas, chemical formulas, tables, etc.▼(However, X is a hydrogen atom or a lower alkyl group. ) or a branched alkyl group, Y represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, an alkoxycarbonyl group, or a trifluoromethyl group, and n is 1
Indicates an integer between ~5. ] A soil disease control agent characterized by containing one or more benzamide derivatives represented by the following as an active ingredient.