KR840000532B1 - Method of prevention of cure for plant diseases - Google Patents

Abstract

The title compd. (I; R=ethyl, isopropyl) was prepd. by the reaction of 2-cyanobenzene sulfonic acid (II') with 2,6-dialkylaniline (III). Thus, 2.01g 2-cyanobenzene sulfonic acidCl was mixed with 3.0g 2,6-diethylaniline at 150oC to give 1.3g 2-cyano-N-(2',6'-diethylphenyl) -benzene sulfonamide (I; R=ethyl). A compn. contg. I (R=ethyl) 20 parts, clay 10 parts, diatomaceous earth 65 parts, lignin sulfonate 3 parts, and polyoxyethylenalkylaryl ether 2 parts (100-150l/10 are) controlled Seath blight in rice. Rice seeds infected with Rhizoctonia type IIIA and treated with 200 ppm I gave 100% germination and 95-100% perfect plants.

Description

Manufacturing method of plant disease releasing agent compound

The present invention relates to novel compounds and their use. More specifically, the present invention relates to a novel benzene sulfonamide derivative and a method for producing a plant disease releasing agent compound using the same as an active ingredient.

At present, antibiotics widely used as a control agent for paperback disease have a low residual effect, which indicates a lack of drug efficacy, and the emergence of resistant bacteria is concerned. On the other hand, organic arsenic is also used as a paperback disease control agent, but since there are heavy metals in the active ingredient, there are many difficulties in existing pharmaceuticals, such as toxic to humans and environmental pollution. In addition, the development of new types of pharmaceuticals is strongly desired from households.

The present invention provides a solution to the above point by providing a novel benzenesulfonamide derivative having plant disease releasing activity. Thus, the 2-cyanobenzenesulfonamide derivative provided by the present invention is of general formula

(Wherein R represents an ethyl group or an isopropyl group, respectively).

Plant disease releasing agent according to the present invention is a general formula

(Wherein R represents an ethyl group or isopropyl group, respectively) as the active ingredient.

The novel compounds according to the present invention generally exhibit control activities against a wide range of agricultural and horticultural crop diseases, but have excellent control effects, in particular, rice paddy disease and stocking diseases of tomatoes and cucumbers.

This novel compound is a very low-toxic synthetic compound that does not contain heavy metals, and its toxicity to humans and fish is practically insignificant, and its weakness against crops is not seen. Therefore, this compound is considered to have sufficient functionality to make up for the shortcomings of the aforementioned conventional drugs.

The compound according to the present invention is represented by general formula (I).

(Wherein R represents an ethyl group or an isopropyl group, respectively. The same for each of the following formulas)

Among the compounds of the general formula (I), those in which R is an ethyl group and an isopropyl group, that is, the following compounds (1) and (2) are typical.

Compound (1)

2-cyano-N- (2 ', 6'-diethylphenyl) benzenesulfonamide.

Compound (2)

2-cyano-N- (2 ', 6'-diethylphenyl) benzenesulfonamide.

The plant disease represented by the formula (1) is characterized by reacting a 2-cyanobenzenesulfonic acid of formula (II ') or a reactive derivative of the hydroxyl group thereof with 2,6-dialkylaniline (III). Method for producing a liberation agent compound.

(Wherein R each represents an ethyl group or isopropyl group, X represents OH or a group which causes the sulfonic acid compound to be a reactive derivative relating to a hydroxyl group).

One suitable method of synthesis is by the reaction shown in the following scheme, which is a reactive derivative of the hydroxyl group of 2-cyinobenzenesulfonic acid, for example halogenides, in particular chloride and 2,6-dialkylaniline (III). ) Is reacted to obtain a target (I).

Since the reaction between the compounds (II) and (III) involves the generation of hydrogen halides, it is preferable to carry out in the presence of an acid trapping agent of various organic bases or inorganic bases. In addition, the reaction can dissolve or disperse at least one of the compounds (I) to (III) and optionally an acid trapping agent to be used in a desired concentration, and furthermore, a solvent or dispersion medium which does not substantially inhibit the reaction. In the presence of i). In that case, an excess amount of compound (III) can be used as an acid trapping agent and a solvent or a dispersion medium.

Specific reaction conditions when performing this reaction, etc. are described in the later experiment and J. Am. Chem. What is necessary is just to select suitably according to the method of Scc, 82, 1594 (1960) (document 1) or Beilstein Handbuch der organishen Chemie XI 376 (document 2). Moreover, compound (II) which is one of raw materials can be synthesize | combined according to the method of description of said J.A.C.S or Beilstein (document 1 or document 2), for example.

The plant disease releasing agent according to the present invention may take any form or mode of use that can be employed as agrohorticultural agent, in particular a fungicide, except that the active ingredient is the above compound.

Specifically, for example, the compound of the present invention is diluted as it is, or diluted with water, a solid powder, or another suitable carrier, and an adjuvant such as an electrodeposition agent is used if necessary, or Alternatively, various liquids or solid carriers may be mixed by methods generally used in the manufacture of pesticides, and if necessary, additives such as a humectant, an electrodeposition agent, a dispersant, an emulsifier, and a fixing agent may be used to hydrate the liquid. (Iii) It can be used in the form of preparations, such as a liquid, an emulsion, powder, and granules.

In the preparation of these preparations, as the liquid carrier, those which can be dispersed or dissolved by a solvent or an adjuvant with respect to the compound of the present invention are used. For example, clay, kaolin, tar, diatomaceous earth, silica, calcium carbonate, calcium bicarbonate and the like are used as solid carriers such as kerosine, acetone, dimethyl sulfoxide, animal and vegetable oils and surfactants.

The content of the active ingredient in the formulation thus obtained can be changed in a wide range. For example, when used as a liquid, the concentration in the liquid is suitably about 10 ppm to 500 ppm, and in the case of powder or granules, it is preferable to contain the compound of the present invention in the range of about 1% to 20%.

Of course, it can be formulated to a higher concentration than such a concentration and can be diluted at the time of use. If the circumstances permit, other compatible horticultural medicines or fertilizers may be mixed for formulation.

The control agent according to the present invention can be used by spraying on the foliage of crops, and can also be used by applying it to the surface of water, water or soil or eaves. In that case, compatible agrohorticultural agents or fertilizers can be mixed. Such agrohorticultural agents include, for example, fungicides, herbicides, plant life regulators and the like.

The dosage varies depending on the type and extent of the disease, the type of crop, the type of application, etc., but when applied to soil, for example, a dosage of about 0.1 kg to 10 kg per 10 are usually appropriate.

Next, as an experimental example

1) Compound is synthesized

Synthesis Example 1 Synthesis of Compound (1)

2.01 g of 2-cyanobenzene sulfonic acid chlorides and 3.0 g of 2,6-diethylaniline were mixed, and it heated at 150 degreeC, stirring. The exothermic reaction reacted, and the clear solution soon solidified. Immediately stop heating, allow to cool, add methanol and precipitate the crystals, filter, wash with a small amount of methanol, and 2-cyano-N- (2 ', 6'-diethylphenyl) -benzenesulfonamide (formula ( In I), 1.3 g of compounds of R = ethyl groups were obtained.

(1) Melting point: 131.5 to 133 ° C (recrystallized solvent methanol).

(2) Infrared absorption spectra (Nujnl) (cm ^-1 ): 3230 (NH), 2260 (C 2N), 1660, 1586, 1406, 1334, 1264, 1192, 1158, 1132, 1068, 1038, 971, 946,684, 606.

(3) NMR Spectrum (DMSO-d6-TMS) δ: 8.05 to 6.68 (7H, multiplet, aromatic ring proton), 2.30 (4H, quadruple, J = 7Hz, -CH ₂ -CH ₃ x 2), 0.93 (6H, triplet, J = 7 Hz, -Ch ₂ -CH ₃ x 2).

(4) Mass Spectrum m / e: 314 (M ⁺ )

(5) Elemental Analysis Value (%): C ₁₇ H ₁₈ N ₂ O ₂ S (314.4)

Calculated Value: C 64. 95, H 5.77, N 8. 91

Analytical Value: C 64. 87, H 5.80, N 8.88

Synthesis Example 2 Synthesis of Compound (2)

6.48 g of 2,6-isopropylaniline and 4.2 g of 2-cyano-benzenesulfonic acid chloride were mixed and the heating was stopped when the contents were completely solidified when the bath temperature reached 120 ° C, and the mixture was allowed to cool and cooled to methanol. 30 ml was added to form a slurry, and the precipitated colorless crystals were filtered, washed with cold methanol, and washed with 2.8 g of 2-cyano-N- (2,6-diisopropylphenyl) -benzenesulfonamide. The crystal of was obtained.

(1) Melting point: 175 to 176.5 ° C. (decomposition), (methanol for recrystallization).

(2) Infrared absorption spectrum (Nujol) (cm ^-1 ): 3240 (NH), 2260 (C≡N), 1589, 1408, 1339, 1260, 1185, 1161, 1131, 1104, 1066, 928, 804, 773 , 756, 703, 688, 625, 600, 571.

(3) NMR Spectrum (DMSO-d6-TMS) δ: 8.05∼6.82 (7H, multiplet, aromatic ring proton), 2.92 (2H, triplet, J = 6.5Hz, -CH (CH ₃ ) ₂ × 2 ), 0.91 (12H, doublet, J = 6.5Hz, CH (CH ₃ ) ₂ × 2)

(4) Elemental Analysis Value (%): C ₁₉ H ₂₂ N ₂ O ₂ S (342.46)

Calculated Value: C 66.63, H 6.48, N 8. 18

Analytical Value: C 66. 56, H 6.52, N 8.13

Mass spectrum m / e: 342 (M ⁺ ), 299 (M ⁺ -CH (CH ₃ ) ₂ , 176

2) Formulation

[Example 1]

Hydrating agent

20 parts by weight of 2-cyano-N- (2 ', 6'-diethylphenyl) │ 65 parts by weight of diatomaceous earth

Benzenesulfonamide │ 3 parts by weight of lignin sulfonic acid

Clay 10 parts by weight │ Polyoxyethylene alkyl aryl ether 2 parts by weight

The above constituent materials are mixed and ground uniformly to form a hydrated composition, and sprayed at a concentration of 100 to 150 l per 10 drops.

[Example 2]

Powder

2-cyano-N- (2 ', 6'-diisopropylphenyl) 3 parts by weight │Silic anhydride powder 1 part by weight

Benzenesulfonamide │ 48 parts by weight of clay

1 part by weight of calcium stearate│ 47 parts by weight of tar

The powder composition obtained by mixing and grinding the above components is sprayed at 4 kg per 10 ares.

[Example 3]

Granulation

8 parts by weight of 2-cyano-N- (2 ', 6'-diisopropylphenyl) | carboxymethyl cellulose

Benzenesulfonamide 3 parts by weight

89 parts by weight of clay

The above-mentioned ingredients are mixed, an appropriate amount of water is added, and after molding, the granulated composition, which is dried, is sprayed with 3 kg per 10 ars.

3) Drug test

[Test Example 1]

Control effect test of rice paddy disease

Chemical spraying device spray gun (3kg / cm ² ) in which the hydration agent prepared in Formulation Example 1 was adjusted to a spraying solution of a predetermined concentration, on rice (variety stone) of a sowing machine grown with a wagner pot of 1/5000 ar. Sprayed at a rate of 70 cnl / 3 pot.

On the day of the inoculation, immediately after the air drying, the agar bacillus obtained by sprinkling the oak germs obtained by a 48-hour incubation on a peptone-available Majeoseo juice agar medium with a 0.5 cm cork bowl was placed at the center of the mark and 15 cm from the surface. Inoculation was performed. In addition, 7 days after spraying to prevent the invasion, the inoculation zone was inoculated in the glass greenhouse for 7 days after spraying the chemical solution and left in the glass greenhouse for 7 days, and then inoculated according to the same method. .

After the inoculation, both inoculated and inoculated 7 days after the inoculation were covered with a vinyl cylinder for each port to promote the invasion of paperback bacteria, and left in a glass greenhouse at 30 ° C. and 24 ° C. at night for 10 days. The length of disease path | route of the pathogenesis was measured, and the control value was computed according to following Formula. At the same time, the situation of weakness was followed by visual observation.

The results are shown in the following table.

[Test Example 2]

Seedling Disease Control Test

Seedling rot bacteria (Li foot Tonnaer bacteria type IIIA bacteria) were cultured on the agar medium of Maryeongseojeon and mixed with three times of rice bran to inoculate. Sowing seeds of 20 grains / pot in 1/5000 arwagner pots containing sterilized foot soil and using soil as a starter It was covered and inoculated by uniformly spreading the same mixture of the inoculation source and the sterilization foot. After inoculation, the mixture of the present invention of Formulation Example 1 was prepared at a predetermined concentration to obtain an irrigation solution, and 100 ml of this chemical solution per pot was uniformly placed on the surface of the surface with pipette. Then, in order to facilitate the invasion and invasion of the inoculation bacteria, it was brought into a glass greenhouse at 30 ° to 28 ° C. and invented by passing the soil in the pot slightly dried. Investigations were conducted on the number of germinations and the number of whole bacteria up to three weeks after sowing, and the germination rate for seeding intake and the total number of whole bacteria for germination were calculated.

The results were as shown in the following table.

Claims (1)

A plant disease-releasing agent compound represented by formula (I), characterized by reacting a 2-cyanobenzenesulfonic acid of formula (II ') or a reactive derivative relating to its hydroxyl group with 2,6-dialkylaniline (III). Recipe.

(Wherein R each represents an ethyl group or isopropyl group, X represents OH or a group which makes the sulfonic acid compound a reactive derivative for hydroxyl groups).