JPS62161761A - N-phenylsulfonylisonicotinamide derivative and agricultural and horticultural fungicide composition containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [X and Y are H or Cl; R is H, lower alkyl or allyl; Z is H, lower alkyl, halogen, nitro, methoxy, methylthio, methylsulfonyl, CF3, phenyl, phnoxy or COOR' (R' is CH3 or C2H5); n is 1-3; excluding the case that X=Y=R=H and Z=CH3]. EXAMPLE:N-(4-fluorophenylsulfonyl)-2-chloroisonicontinamide. USE:An active component for agricultural and horticultural fungicide composition. It exhibits high fungicidal effect and can be used as an agricultural and horticul tural fungicide for paddy field, plowed land, orchard, etc., without causing adverse effect such as phytotoxicity to plant. PREPARATION:The compound of formula I can be produced e.g. by reacting a benzenesulfonamide compound of formula II with isonicotinic acid chloride of formula III in a solvent such as ethyl acetate in the presence of an acid acceptor such as triethylamine at room temperature -180 deg.C.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel N-phenylsulfonylisonicotinic acid amide derivative, which can be used as an agricultural and horticultural fungicide in paddy fields, fields, orchards, etc. I can do it.

[Conventional technology]

Conventional agricultural fungicides include antibiotics, organic phosphorus agents, organic synthetic fungicides, etc.0 Also, U.S. Patent No. 2,270,200
No. 1 discloses the compound Seishin')-coNHsoz%cHs and states that this compound is useful as a treatment for coccal infections. However, there is no description that this compound is useful as an agricultural and horticultural fungicide such as a rice blast control agent.

[Problem that the invention seeks to solve]

Conventional fungicides for agriculture and horticulture are insufficiently effective against bacterial diseases such as rice blast, rice blight, and cucumber spot, or have problems with drug-resistant bacteria or cause chemical damage to crops. It also has drawbacks such as problems with economic efficiency.

The present invention provides a useful agricultural and horticultural fungicide that overcomes these drawbacks.

[Means for solving problems]

The present inventors have demonstrated that by using an N-fersulfonylisonicotinic acid amide derivative represented by the following formula (1), it is possible to overcome the drawbacks of conventional agricultural and horticultural fungicides, to obtain a high pest control effect, and to improve plant health. The present invention was completed by discovering that this method does not cause any adverse effects such as drug damage.

[In the formula, X and Y are hydrogen atoms or chlorine atoms which may be the same or different, R is a hydrogen atom, a lower alkyl group or an allyl group, and Z is a hydrogen atom or a lower alkyl group.]
rogen atom, nitro group or methoxy group, methylthio group,
It represents a methylsulfonyl group, a trifluoromethyl group, a phenyl group, a phenoxy group, a COOR group (R represents a methyl group or an ethyl group). n represents an integer of 1 to 3. ] The compound of formula (1) of the present invention can be created by the following method.

(81 formula % formula % (2) (wherein, R, Z, n have the same meanings as above), a benzenesulfonamide compound represented by the formula (wherein, X, Y have the same meanings as above), It can be obtained by reacting with isonicotinic acid chloride represented by ) in the presence of a solvent, optionally in the presence of a deoxidizing agent.

Examples of deoxidizers mentioned here include alkali metal hydroxides (NaOH, KOH, etc.), alkaline earth metal hydroxides (Ca(OH)2, Mg(OH)2, etc.),
Alkali metal alcolade (such as sodium alcolade), alkali metal hydride (such as sodium hydride)
, alkali metal fluorides (such as cesium fluoride), alkali metal carbonates (such as soda ash), sodium hydroxide, ramamide,
Examples include bases such as trialkylamines (triethylamine, etc.), dialkylanilines (dimethylaniline, diethylaniline, etc.), aliphatic and aromatic tertiary amines such as hyridine.

In addition to the bases mentioned above, metallic copper can also be used as a deoxidizing agent.

Examples of solvents include organic solvents, such as aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as hexane, heptane, and petroleum dichloromethane, halogen hydrocarbons such as chloroform dichloromethane, and non-proton-donating hydrocarbons such as dimethylformamide and dimethyl sulfoxide. polar solvent, diisopropyl ether, diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran,
Ethers such as dioxane, nitriles such as acetonitrile and propionitrile, ketones such as acetone and diisopropyl ketone, and esters such as ethyl acetate can be used.

The reaction temperature is room temperature to 180°C, preferably 80°C to 120°C.
C., the starting materials are preferably used in equimolar ratios, and in rare cases it may be advantageous to use an excess of one or the other of the reaction components.

The reaction mixture is obtained in customary manner, for example by adding water and separating the phases. The crude product can be purified by recrystallization or column chromatography.

(bl) The compound of formula (1) can also be produced by the following method (wherein, X, Y, Z, and n have the same meanings as above). By reacting with this benzenesulfonyl isocyanate in the benzenesulfonyl isocyanate (11), an N-phenylsulfonylisonicotinic acid amide derivative can be obtained.

As the solvent, hydrocarbons such as acetonitrile, ether, toluene, norogenated aliphatic or aromatic hydrocarbons, and mixtures of these solvents are used.The reaction temperature is room temperature to 180°C, preferably 40°C. '~1
It can be carried out at 50°C.

(Cl) The compound of formula (1) can be further prepared by the following method (wherein R" represents an alkyl group or an aryl residue,
, Y,' R, Z and n have the same meanings as above.

) In this method, N-phenylsulfonylisonicotinic acid amide derivatives are obtained by reacting isonicotinic acid esters with benzenesulfonamides in the presence of a base in the presence of a solvent or in the absence of a solvent. be able to.

Acetonitrile, alcohol, etc. are used as the solvent, and the reaction temperature is 40°C to 200°C, preferably 60°C.
It can be carried out at ~180°C. Examples of the base include alkali carbonates (potassium carbonate, etc.) and alkali metal alcoholades (sodium methylate, etc.).

(dl In formula (1), when R is a lower alkyl group or an allyl group, a compound represented by the formula (X, Y, Z and n have the same meanings as above) is added to an alkali metal in the presence of a solvent. R-Q (
It can also be obtained by reacting with (R means the same as above and Q represents a halogen atom).

Here, as the solvent, ethers such as diethyl ether and tetrahydrofuran, aprotic polar solvents such as dimethyl sulfoxide and dimethyl formamide are used, and the reaction temperature is -20°C to 150°C, preferably 0°C to 10°C.
It can be carried out at 00°C.

When using the compound of the present invention as an active ingredient of a fungicide for agriculture and horticulture, one or more compounds of the present invention may be used.

When the compound of the present invention is used as a fungicide for agricultural and horticultural purposes, depending on the purpose of use, it may be used as is, or it may be mixed with an agrochemical adjuvant to enhance or stabilize the effect, using methods commonly used in the field of agrochemical manufacturing. Accordingly, it can be used in the production form of powders, fine granules, granules, wettable powders, flowable preparations, emulsions, etc.

In actual use, these various formulations can be used directly or diluted with water to a desired concentration.

The agrochemical auxiliary agents mentioned herein include carriers (diluents) and other auxiliary agents such as spreading agents, emulsifiers, wetting agents, dispersants, fixing agents, and disintegrants.

Liquid carriers include aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, butanol, and glycol, ketones such as acetone, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, methylnaphthalenecyclohexane, and animal and vegetable oils. , fatty acids, fatty acid esters, etc.

Solid carriers include clay, kaolin, talc, diatomaceous earth,
Examples include silica, calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina, and sawdust.

In addition, surfactants are usually used as emulsifiers or dispersants, such as anionic surfactants such as higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyshetylene alkylphenyl ether, lauryl betaine, and cationic surfactants. surfactants, nonionic surfactants, and amphoteric surfactants.

Spreading agents include polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, etc. Wetting agents include polyoxyethylene nonylphenyl ether, dialkyl sulfosuccinate, etc., and fixing agents include carboxymethyl cellulose, polyvinyl alcohol, etc. However, examples of disintegrants include genin sulfone fl/l sodium and sodium lauryl sulfate.

Not only can each formulation be used alone, but
It can also be used in combination with other agricultural and horticultural fungicides, insecticides, plant growth regulators, and acaricides.

The active ingredient compound content in the agricultural and horticultural fungicide of the present invention is:
It varies depending on the formulation form, method of application, and other conditions, and in some cases only the active ingredient compound may be used, but it is usually in the range of 0.5 to 95% (by weight), preferably 2 to 70% (by weight).

〔Effect of the invention〕

The compound of the present invention exhibits high control effects on rice diseases such as rice blast, rice bacterial leaf blight, and rice blight, as well as bacterial diseases such as cucumber spot bacterial disease, using both soil application and foliage spraying methods. This is a fungicide that is effective against drug-resistant bacteria and does not cause harmful effects such as phytotoxicity on plants.

〔Example〕

The present invention will be explained below with reference to Examples.

Synthesis Example Synthesis Example 1゜N-(4-methylphenylsulfonyl)-1sonicotinic acid amide (compound number 2) 17) Production: 3.7 g of isonicotinic acid 6 g of top-p-toluenesulfonyl isocyanate
While stirring vigorously, gradually heat the mixture to 125°-130°.
The reaction was allowed to proceed at ℃ until the bubbling of carbon dioxide gas stopped. (3
0 minutes to 1 hour) The solidified crude product was taken out, crushed and washed with 39 ml of ethyl acetate to obtain 6.1 ml of N-(4-methylphenylsulfonyl)-isonicotinic acid amide.
g (yield 73.6%) is a white crystal (m, p249°~2
51°C).

Synthesis Example 2 Production of N-(4-fluorophenylsulfonyl)-2-chloroisonicotinic acid amide (Compound No. 7): 1.75 g of p-fluorobenzenesulfonamide was dissolved in 20 ml of ethyl acetate, and 1.75 g of triethylamine was dissolved. 1
Add g. A solution of 1.76 g of 2-chloroisonicotinic acid chloride in ethyl acetate was added dropwise to this solution at room temperature, and after the dropwise addition was completed, the mixture was further stirred at room temperature for 1 hour. Subsequently, 20 ml of xylene was added, and the mixture was heated under reflux for 4.5 hours.

After cooling, water was added to remove the precipitated inorganic salt, and the organic layer was dried and concentrated to obtain 2.74 g of crystals of the crude product. By recrystallizing this from ethyl acetate, N-(4-fluorophenylsulfonyl)-2-10
Leisonicotinic acid amide 2.09g (yield 66.5%)
was obtained as white crystals (m, p 195-197°C).

Synthesis example 3°N -7! Preparation of J sil--phenylsulfonyl-2,6-dichloroisonicotinic acid amide (compound no. 16): 0.3 g of 60% sodium hydride in 30 ml of benzene
N-allylbenzenesulfonamide 1.
47 g of benzene solution are added dropwise at room temperature. After stirring for a while, 2.6-dichloroisonicotinic acid chloride 1
．． 56 g of benzene solution was added to the solution at room temperature, and after the dropwise addition was completed, the mixture was further stirred for 2 hours. After adding water, removing salt and washing the organic layer with a dilute aqueous hydrochloric acid solution and a dilute aqueous hydrochloric acid solution, drying, and distilling off the solvent under reduced pressure, the crude product crystals 2.7.3
g was obtained. This was recrystallized from benzene to give 2.15 g (yield 78.2%) of N-allyl-N-phenylsulfonyl-2,6-dichloroisonicotinic acid amide as white crystals (m, p 118.5-119°C). ) was obtained.

Further compounds of the present invention were synthesized by the methods of Synthesis Examples 1 to 3.

Representative ones are shown in Table 1.

Synthesis Example 4 Synthesis of N-(2-piphenylsulfonyl)-2-chloroisonicotinic acid amide (compound number 20); 2-chloroisonicotinic acid 3-7'tylphenyl ester 2.4 g (0,01 mol), 2.3 g (0.01 mol) of 2-piphenylsulfonamide and 1.4 g (0.01 mol) of anhydrous potassium carbonate at 120-130
Melt with stirring at °C. After 30 minutes to 1 hour, when the generation of carbon dioxide gas has stopped, add 5Qml of water, and then add concentrated hydrochloric acid dropwise.
Add until acidic. Extract with ethyl acetate, dry the organic layer, and then concentrate to obtain crude crystals. By recrystallizing this from a mixed solvent of n-hexane and ethyl acetate, 1.6 g (yield 42.9%) of N-(2-piphenylsulfonyl)-2-chloroisonicotinic acid amide was obtained as white crystals. can get.

Synthesis example 5゜N-(4-methylsulfonylphenylsulfo=yv
) -2-chloroisonicotinic acid amide (compound tooth 22
) Synthesis: 2.3 g (0.01 mol) of 4-methylsulfonylbenzenesulfonamide was completely dissolved in 20 mt of helicin, and 2-chloroisonicotinic acid chloride 1.
7 g (0.01 mol) was added dropwise and the mixture was further stirred at room temperature for 2 hours. Aqueous hydrochloric acid solution is added to make the mixture acidic, and the precipitate is extracted with ethyl acetate.

After drying the organic layer, the precipitated crude crystals are recrystallized from n-hexane-ethyl acetate. -K.J.
:S,N-(4-methylsulfonylphenylsulfonyl)-2-10 leisonicotinic acid amide 2.8g (yield 7
4.7%) are obtained as white crystals.

Synthesis Example 6 Synthesis of N-(4-chloro-2-)IJfluoromethylphenylsulfonyl)-2-10 leusonicotinic acid amide (compound 31): In 20 ml of pyridine, 4-chloro-2-trifluoromethylbenzene 2.6 g of sulfonamide (0.01 mo/
2-chloroisonicotinic acid chloride is added dropwise at room temperature. After dropping, add 2 more times at room temperature.
Stir for an hour. Aqueous hydrochloric acid solution is added to make the mixture acidic, and the precipitate is extracted with ethyl acetate. After drying the organic layer, concentrate
By recrystallizing the precipitated crude crystals from a mixed solvent of n-hexane and ethyl acetate, N-(4-chloro-2-t!) was obtained.
3.4 g (yield: 85.1%) of J fluoromethylphenylsulfonyl)-2-chloroisonicotinic acid amide are obtained as white crystals.

Further compounds of the present invention were synthesized by the methods of Synthesis Examples 4 to 6.

Representative ones are shown in Table 1.

Table 1 Formulation Examples Formulation examples are shown below, but the types and mixing ratios of agricultural chemical adjuvants are not limited to these, and can be used in a wide range. Note that "parts" means "parts by weight."

Formulation example 1. Powder FlZ Compound No. 11 No. 4 2 parts of N-allyl-N-phenylsulfonyl-2-chloroisonicotinic acid amide and 98 parts of clay are mixed and ground to obtain a powder.

Formulation example 2. Wettable powder Compound No. 13 20 parts of N-phenylsulfonyl-2,6-dichloroisonicotinic acid amide, 75 parts of kaolin, 3 parts of higher alcohol sodium sulfate, and 2 parts of sodium ligninsulfonate are mixed and ground to prepare a wettable powder. .

Formulation Example 33 granules Compound No. 7 8 parts of N-(4-fluorophenylsulfonyl)-2-chloroisonicotinic acid amide, diatom ±36
part, 24 parts of bentonite, 30 parts of talc and 2 parts of disintegrant.
After mixing 18 parts of water, add 18 parts of water to make it evenly wet, then extrude it through an injection molding machine, granulate it, size it with a sizing machine, and then dry it to form particles with a particle size of 0.6# to 1wn. as a drug.

Formulation Example: 4 parts Microgranules Compound No. 3 5 parts of N-phenylsulfonyl-2-chloroisonicotinic acid amide was uniformly mixed and pulverized with 1 part of polyvinyl alcohol and 14 parts of clay to form a thick powder. Separately 74~105μ oil well absorbent mineral coarse powder 80
1 part is placed in a suitable mixer and while rotating, add 15 parts of water to moisten it, add the above-mentioned thick powder, coat it and dry it to make fine granules. Formulation Example 5. Emulsion compound number 2N-(4-methylphenylsulfonyl)-
30 parts of innicotinamide was dissolved in 52 parts of xylene, and a mixture of alkylphenol ethylene oxide condensate and calcium alkylbenzenesulfonate (8:
2) Mix and dissolve 18 parts to make an emulsion.

The basic rule is to dilute it with water and use it as an emulsion.

Next, it will be explained using experimental examples that the active ingredient compound of the present invention has excellent control effects against various agricultural and horticultural crop diseases.

Experimental exampleExperimental example Work, rice blast control test (soil application) Fresh 1
1crn, width 5crn, height 10c! Rice (variety: Saitama Mochi No. 10) was grown for two weeks in a plastic pot of No. ,7
After a few days, rice blast fungus (Pyricularia or
yzae) was spray-inoculated, kept in a greenhouse at 23°C for 2 days, and then allowed to develop in the greenhouse. 10 days after inoculation, the degree of disease onset was investigated, and the control value was calculated using the following formula. The results are shown in Table 2. Note that IBP granules (active ingredient: S-benzyl diisopropyl phosphorothiolate) were used as a control drug.

0: No lesions observed at all.

1: Slight lesions are observed.

Disease severity: 2: Many lesions are observed.

3: Very many lesions and a few dead leaves are observed.

4: Many dead leaves are observed.

5: Very many dead leaves are observed.

Table 2 Rice blast control test 1 (soil application) Experiment example 2
．． Rice blast control test (spraying on foliage) 11crn
Rice (variety: Saitama Mochi No. 10) was grown for two weeks in a plastic pot with a width of 1 Qcrn and a height of 10 crr1, and the rice was treated with water containing the compound of the present invention prepared by the method of Example 2 as an active ingredient. A medicinal solution of a predetermined concentration obtained by diluting the Japanese preparation was sprayed on foliage. After air-drying, spray inoculation with a spore suspension of rice blast fungus (Pyricularia oryzae), keep in a greenhouse at 23℃ for 2 days, let the disease develop in the greenhouse, examine the degree of disease onset 10 days after inoculation, and control using the following formula. The value was calculated. The results are shown in Table 3.

In addition, IBP emulsion (active ingredient: S-benzyl diisopropyl phosphorothiolate) was used as a control drug.

0: No lesions observed at all.

1; Slight lesions observed.

2: Many lesions are observed.

Disease severity: 3: Very many lesions and a few dead leaves are observed.

4: Many dead leaves are observed.

5: Very many dead leaves are observed.

Table 3 Rice blast control test (foliar spraying) Experimental example 3.
Rice leaf blight control test (soil application) fresh 15crn1
Rice (variety: Musashi Kokane) was grown for one and a half months in a plastic pot with a width of 5 crn and a height of 10 crn.

A predetermined amount of the granules of the compound of the present invention prepared by the method of Formulation Example 3 was applied to the soil of this rice, and two days later, the rice leaves were infected with Xanthomonas campestris.
p-v-oryzae) was inoculated into the front leaves, kept in a greenhouse at 30°C for 24 hours to infect the plants, and then allowed to develop disease in the greenhouse. 21 days after inoculation, lesions were investigated.

The results are shown in Table 4. As a control drug, probenazole granules (active ingredient: 1,2-benzisothiazol-3-one-1,1-dioxide) were used.

Claims (2)

[Claims] (1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, X and Y represent a hydrogen atom or a chlorine atom, which may be the same or different, and R represents a hydrogen atom, lower alkyl group, or allyl group. Z is a hydrogen atom, a lower alkyl group, a halogen atom, a nitro group, a methoxy group, a methylthio group, a methylsulfonyl group, a trifluoromethyl group, a phenyl group, a phenoxy group, or a COOR group (R is a methyl group or an ethyl group) ) is shown. n represents an integer of 1 to 3. However, X,
Except when Y and R are both hydrogen atoms and Z is a methyl group. ] An N-phenylsulfonylisonicotinic acid amide derivative represented by: (2) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, X and Y represent a hydrogen atom or a chlorine atom, which may be the same or different, and R represents a hydrogen atom, a lower alkyl group, or an allyl group. Z is a hydrogen atom, a lower alkyl group, a halogen atom, a nitro group, a methoxy group, a methylthio group, a methylsulfonyl group, a trifluoromethyl group, a phenyl group, a phenoxy group, or a COOR group (R is a methyl group or an ethyl group) ). n represents an integer of 1 to 3. ] An agricultural and horticultural fungicide composition containing an N-phenylsulfonylisonicotinic acid amide derivative represented by the following as an active ingredient.