JPH0733609A - Agricultural/horticultural bactericide - Google Patents

Abstract

PURPOSE:To provide the a highly stable bactericide, low in chemical injury, having excellent ahtibacterial activity on various plant pathogenic bacteria, thus suitably useful for control of various plant disease injuries. CONSTITUTION:The bactericide containing, as active ingredient, an N-benzyl-N- phenoxyethylammonium salt of the formula (W, X, Y and Z are each H, halogen, NO2 or 1-4C alkyl; V<-> is halogen, nitrate, sulfate, phosphate or acetate ion), e.g. N-benzyl-N,N-dimethyl-N-2-phenoxyethylammonium chloride. The compound of the formula has powerful bacteriostatic or bactericidal activity on Xanthomonas bacteria such as canker, Clavibacter bacteria such as bacterial canker, Pseudomonas bacteria such as bacterial spot, and Erwinia bacteria such as bacterial soft rot.

Description

Detailed Description of the Invention

[0001]

The present invention relates to agricultural chemicals containing N-benzyl-N-phenoxyethylammonium salt, more specifically N-substituted benzyl-N- [2- (substituted phenoxy) ethyl] dimethylammonium salt, as an active ingredient. A horticultural germicide.

[0002]

2. Description of the Related Art Inorganic or organic copper agents, and antibiotic agents such as streptomycin have been conventionally used as fungicides against pathogenic bacteria of diseases of agricultural crops. However, these conventional agents have problems in that the efficacy is not sufficient in practical use and the occurrence of phytotoxicity. Therefore, further bacteriostatic action or bactericidal action (these are collectively referred to as “antibacterial action”) (Sometimes noted)
There is a demand for a drug that is strong and causes less phytotoxicity.

[0003]

The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems of the prior art, and as a result, N-benzyl-N-phenoxyethylammonium salt, specifically N The present invention has been accomplished by discovering that -substituted benzyl-N- [2- (substituted phenoxy) ethyl] dimethylammonium salt has a bacteriostatic action or bactericidal action against pathogenic bacteria of agricultural and horticultural diseases. That is, the present invention relates to an agricultural and horticultural fungicide containing as an active ingredient at least one of the N-benzyl-N-phenoxyethylammonium salts shown in Chemical formula 2.

[0004]

[Chemical 2] [In the formula, W, X, Y, and Z represent hydrogen, halogen, nitro, or a lower alkyl group having 1 to 4 carbon atoms, and V ⁻ represents halogen, nitric acid, sulfuric acid, phosphoric acid, or acetate ion]

Specific examples thereof include the following compounds. Compound 1; N-benzyl-N, N-dimethyl-N-2-
Phenoxyethyl ammonium chloride compound 2; N-2-chlorobenzyl-N, N-dimethyl-N-2-phenoxyethyl ammonium chloride compound 3; N-3-chlorobenzyl-N, N-dimethyl-N-2-phenoxyethyl Ammonium chloride compound 4; N-4-chlorobenzyl-N, N-dimethyl-N-2-phenoxyethyl ammonium chloride compound 5; N, N-dimethyl-N-2-methylbenzyl-N-2-phenoxyethyl ammonium bromide Compound 6; N, N-dimethyl-N-3-methylbenzyl-N-2-phenoxyethylammonium bromide Compound 7; N, N-dimethyl-N-4-methylbenzyl-N-2-phenoxyethylammonium chloride Compound 8 N-2,4-dichlorobenzyl-N, N-di Methyl-N-2-phenoxyethylammonium chloride compound 9; N-3,4-dichlorobenzyl-N, N-dimethyl-N-2-phenoxyethylammonium chloride compound 10; N-2,6-dichlorobenzyl-N, N-
Dimethyl-N-2-phenoxyethylammonium bromide compound 11; N, N-dimethyl-N-4-nitrobenzyl-N-2-phenoxyethylammonium bromide compound 12; N-2-chlorobenzyl-N-2- (2 −
Chlorophenoxy) ethyl-N, N-dimethylammonium chloride Compound 13; N-3-chlorobenzyl-N-2- (2-
Chlorophenoxy) ethyl-N, N-dimethylammonium chloride Compound 14; N-4-chlorobenzyl-N-2- (2-
Chlorophenoxy) ethyl-N, N-dimethylammonium chloride Compound 15; N-2,4-dichlorobenzyl-N-2-
(2-Chlorophenoxy) ethyl-N, N-dimethylammonium chloride Compound 16; N-3,4-dichlorobenzyl-N-2-
(2-Chlorophenoxy) ethyl-N, N-dimethylammonium chloride Compound 17; N-2,6-dichlorobenzyl-N-2-
(2-Chlorophenoxy) ethyl-N, N-dimethylammonium bromide compound 18; N-2- (2-Chlorophenoxy) ethyl-N, N-dimethyl-N-4-nitrobenzylammonium bromide compound 19; N-benzyl -N-2- (3-chlorophenoxy) ethyl-N, N-dimethylammonium chloride Compound 20; N-2-chlorobenzyl-N-2- (3-
Chlorophenoxy) ethyl-N, N-dimethylammonium chloride Compound 21; N-3-chlorobenzyl-N-2- (3-
Chlorophenoxy) ethyl-N, N-dimethylammonium chloride Compound 22; N-4-chlorobenzyl-N-2- (3-
Chlorophenoxy) ethyl-N, N-dimethylammonium chloride Compound 23; N-2,4-dichlorobenzyl-N-2-
(3-Chlorophenoxy) ethyl-N, N-dimethylammonium chloride Compound 24; N-3,4-dichlorobenzyl-N-2-
(3-chlorophenoxy) ethyl-N, N-dimethylammonium chloride compound 25; N, N-dimethyl-N-4-nitrobenzyl-N-2- (3-chlorophenoxy) ethylammonium bromide compound 26; N-2 -Chlorobenzyl-N-2- (4-
Chlorophenoxy) ethyl-N, N-dimethylammonium chloride Compound 27; N-3-chlorobenzyl-N-2- (4-
Chlorophenoxy) ethyl-N, N-dimethylammonium chloride Compound 28; N-4-chlorobenzyl-N-2- (4-
Chlorophenoxy) ethyl-N, N-dimethylammonium chloride Compound 29; N-2- (4-chlorophenoxy) ethyl-N, N-dimethyl-N-2-mailbenzylammonium bromide Compound 30; N-2- (4 -Chlorophenoxy) ethyl-N, N-dimethyl-N-3-methylbenzylammonium bromide compound 31; N-2- (4-chlorophenoxy) ethyl-N, N-dimethyl-N-4-methylbenzylammonium chloride compound 32; N-2,4-dichlorobenzyl-N-2-
(4-Chlorophenoxy) ethyl-N, N-dimethylammonium chloride Compound 33; N-3,4-dichlorobenzyl-N-2-
(4-Chlorophenoxy) ethyl-N, N-dimethylammonium chloride Compound 34; N-2,6-dichlorobenzyl-N-2-
(4-chlorophenoxy) ethyl-N, N-dimethylammonium bromide compound 35; N-benzyl-N-2- (2,4-dichlorophenoxy) ethyl-N, N-dimethylammonium bromide compound 36; N-2- Chlorobenzyl-N-2- (2,
4-Dichlorophenoxy) ethyl-N, N-dimethylammonium chloride Compound 37; N-3-chlorobenzyl-N-2- (2,2
4-Dichlorophenoxy) ethyl-N, N-dimethylammonium chloride Compound 38; N-4-chlorobenzyl-N-2- (2,2
4-Dichlorophenoxy) ethyl-N, N-dimethylammonium chloride Compound 39; N-2,4-chlorobenzyl-N-2-
(2,4-Dichlorophenoxy) ethyl-N, N-dimethylammonium chloride Compound 40; N-3,4-chlorobenzyl-N-2-
(2,4-Dichlorophenoxy) ethyl-N, N-dimethylammonium chloride Compound 41; N-2,6-chlorobenzyl-N-2-
(2,4-Dichlorophenoxy) ethyl-N, N-dimethylammonium bromide compound 42; N-2- (2,4-dichlorophenoxy)
Ethyl-N, N-dimethyl-4-nitrobenzylammonium bromide compound 43; N-benzyl-N-2- (3,4-dichlorophenoxy) ethyl-N, N-dimethylammonium bromide compound 44; N-2,4 -Chlorobenzyl-N-2-
(3,4-Dichlorophenoxy) ethyl-N, N-dimethylammonium chloride Compound 45; N-3,4-chlorobenzyl-N-2-
(3,4-Dichlorophenoxy) ethyl-N, N-dimethylammonium chloride The above compound group is 2- (substituted phenoxy) ethyl-N, N.
-It can be synthesized by reacting dimethylamine and benzyl halide.

The N-benzyl-N-phenoxyethylammonium salt of the present invention can be used to treat Xanth of citrus ulcer disease and the like.
omonas bacteria, Clavibacter bacteria such as tomato ulcer, Pseudomonas bacteria such as cucumber spot bacteria,
In addition to showing strong bacteriostatic action or bactericidal action against Erwinia genus bacteria such as Chinese cabbage soft rot fungus, it also shows a strong antibacterial action against pathogenic bacteria of other crop diseases.
All of these N-benzyl-N-phenoxyethylamines are chemically stable and can withstand long-term storage. Therefore, agricultural and horticultural germicides containing these N-benzyl-N-phenoxyethylamines as active ingredients are highly practical. For example, citrus ulcer disease, rice leaf blight, peach perforation bacterial disease, cabbage black rot, lettuce spot bacterial disease, melon brown spot bacterial disease, soybean leaf blight, cucumber spot bacterial disease, Chinese cabbage soft rot, rice hulls It is effective in controlling a wide range of diseases caused by various pathogens such as bacterial diseases and tomato ulcer diseases. In particular, it has an excellent effect on citrus ulcer disease.

The agricultural and horticultural fungicides of the present invention have been conventionally used by methods known per se, such as wettable powders, liquids, emulsions, flowable (sols), powders, driftless (DL) powders and granules. It can be prepared in any dosage form that can be adopted as an agricultural and horticultural drug, especially as a bactericide. As the carrier used in these preparations, those commonly used in agricultural and horticultural chemicals can be used without any particular limitation. For example, typical examples of the solid carrier include mineral powders such as kaolin, bentonite, clay, talc and vermiculite, plant powders such as wood flour, starch and crystalline cellulose, petroleum resin, polyvinyl chloride, ketone resin and dammal gum. Polymer compounds.

Typical examples of the liquid carrier are water, alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, butanol, ethylene glycol and benzyl alcohol, toluene, benzene, xylene, ethylbenzene and methyl. Aromatic hydrocarbons such as naphthalene, halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloromethane, chloroethylene, monochlorobenzene, trichlorofluoromethane and dichlorofluoromethane, ethers such as ethyl ether, ethylene oxide and dioxane. , Acetone, methyl ethyl ketone,
Ketones such as cyclohexanone and methyl isobutyl ketone, esters such as ethyl acetate, butyl acetate and ethylene glycol acetate, acid amides such as dimethylformamide and dimethylacetamide, sulfoxides such as dimethyl sulfoxide, ethylene glycol monomethyl ether and ethylene glycol mono Alcohol ethers such as ethyl ether, n-
These include aliphatic or alicyclic hydrocarbons such as hexane and cyclohexane, industrial gasoline such as petroleum ether and solvent naphtha, and petroleum fractions such as paraffins, kerosene and gas oil.

Further, various surfactants can be used. Typical examples are nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene alkyl ester, anionic surfactants such as alkylbenzene sulfonate and alkyl sulfate, cationic surfactants such as laurylamine and stearyltrimethylammonium chloride. Examples include activators and amphoteric surfactants such as betaine carboxylic acids and sulfates.

The content of the compound of the present invention in the above-mentioned preparation is not particularly limited, but in practice, it is usually 0.001 to 95 wt%.
It is about 0.01 to 90% by weight. For example, in practice, it is usually about 0.01 to 5 wt% for powders, DL powders and granules, and about 1 to 75 wt% for wettable powders, liquids and emulsions. The preparation thus prepared is applied as it is for powders, driftless agents, granules and the like, and for wettable powders, liquids, emulsions and flowable agents, it is diluted with water or an appropriate solvent and applied. To be done.

The agricultural and horticultural fungicides of the present invention can be used in combination with other agricultural and horticultural fungicides, herbicides, insecticides and plant growth regulators and fertilizers. The fungicide for agricultural and horticultural use of the present invention is applied to the foliage of a crop as it is, or after diluting it, or is applied to the surface of water, water, the surface of soil or the inside of soil.

The application rate of the fungicide for agricultural and horticultural use of the present invention depends on the type of target disease, the degree of disease, the type of target crop, the site of application,
The compound represented by Chemical formula 2 of the present invention is a powder, a driftless agent, and a granule per 10 ares (all of which are active ingredients), although it cannot be unconditionally specified because it varies depending on the application method, application time, type of dosage form, and the like. At a concentration of 3 wt%)
The weight is 6 kg, and in the case of wettable powders, liquids, emulsions and flowable agents (all of which have an active ingredient concentration of 20 wt%), 0.05-
3 kg is diluted with 100-500 l of water and used. The compound of the present invention has a strong antibacterial action, and since it has a large stability, its application period is wide, and not only the treatment of crop diseases,
It can also be used for prevention.

[0013]

EXAMPLES The present invention will be described more specifically by way of examples. The invention is not limited to these examples.

Formulation Example 1 (wettable powder) Compounding ingredients Parts by weight Compound 1 20 Lignin sulfonic acid 3 Polyoxyethylene alkylallyl ether 2 diatomaceous earth 75 Hydration containing 20% by weight of active ingredient by uniformly mixing the above ingredients I got an agent.

Formulation Example 2 (powder) Compounding parts by weight Compound 1 3 Calcium stearate 1 Silicic acid powder 1 Clay 48 Talc 47 The above components were uniformly mixed to obtain a powder containing 3% by weight of the active ingredient.

Test Example 1 Citrus ulcer disease control test A leaf piece of about 1 cm square was cut from a citrus leaf, the leaf piece was immersed in a chemical solution prepared to a predetermined concentration for 20 minutes, the leaf piece was taken out from the chemical solution, and the chemical solution was air-dried. The ulcer bacterial suspension (about 10 ⁸ / ml) was inoculated with a needle. The inoculated leaf pieces were placed in a Petri dish lined with damp filter paper, incubated at 28 ° C. for 10 days, and the disease onset was investigated, and the morbidity was calculated according to the following formula. The occurrence of drug damage was determined by visual observation. The results are shown in Table 1.

[0017] In the above equation, n ₀ : number of leaf pieces with disease occurrence index 0 (no disease occurrence) n ₁ : number of leaf pieces with disease occurrence index 1 (small disease occurrence) n ₂ : number of leaf pieces with disease occurrence index 2 (during disease occurrence) n ₃ : disease occurrence index 3 ( Number of leaf pieces N: Number of leaf pieces investigated

[0018]

[Table 1] Table 1 Citrus ulcer disease control test compound number Concentration (ppm) Susceptibility (%) Drug damage ^** 1 500 0-2500 0-125 1.6-3500 0-250 25.3-125 33.3-12500 0-250 0 − 125 16.7 − 18 500 0 − 250 0 − 125 33.3 − 22 500 0 − 250 0 − 125 5.7 − 24 500 0 − 250 25.3 − 125 33.3 − 28 500 0 − 250 0 − 125 16.7 − 29 500 0 − 250 0 − 125 33.3 − 34 500 0 − 250 16.7 − 125 25.3 − 40 500 0 − 250 0 − 125 16.7 − Cosite wettable powder ^* 2000-fold dilution 30.3 ± no treatment 66.7 * Commercial control drug (2000-fold dilution is copper concentration About 2
70ppm) **-: No drug damage ±: Minor but drug damage +: Drug damage (same as below)

Test Example 2 Rice White Leaf Blight Control Test A 5-leaf stage rice (cultivar Koshihikari) grown in a pot with a diameter of 6 cm was sprayed with an aqueous solution of the test compound prepared to a predetermined concentration. One day later, a leaf blight fungus suspension of rice adjusted to 10 ⁸ / ml was inoculated with leaf scissors. The lesion length was measured 3 weeks after the inoculation, and the control value was calculated according to the following formula.

[0020] The results are shown in Table 2.

[0021]

[Table 2] Table 2 Rice White Leaf Blight Control Test Compound No. Concentration (ppm) Control value (%) Chemical damage 1 500 83.7-12 500 67.3-35 500 72.1-40 500 67.1- Phenazine wettable powder ^* 500-fold dilution 60.1- * Commercial control drug

Test Example 3 Controlling Soft Rot Disease A radish disc having a diameter of 2 cm and a thickness of 1 cm was prepared and immersed in a chemical solution adjusted to a predetermined concentration for 1 hour. The radish disc was taken out from the aqueous solution of the test compound, air-dried, and the bacterial solution was suspended in the center of the disc and kept at 28 ° C for 24 hours, then the disease degree was investigated and the control value was calculated according to the following formula. It was calculated.

[0023] The results are shown in Table 3.

[0024]

[Table 3] Table 3 Soft rot control test compound number Concentration (ppm) Control value (%) Chemical damage 1 400 95 − 12 400 85 − 21 400 90 − 34 400 85 − 43 400 85 − Coside wettable powder ^* 2000-fold dilution 80 ± * Marketed control drug

[0025]

INDUSTRIAL APPLICABILITY The N-benzyl-N-phenoxyethylammonium salt of the present invention is easy to produce, has a large stability, is less harmful to chemicals, and exhibits an excellent antibacterial action against various plant pathogens. Therefore, the fungicide for agricultural and horticultural use of the present invention is suitably used for controlling various plant diseases.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Jiro Tsubouchi Niigata City, Niigata City, Tayuhama, Niiwari 182, Niigata Research Center Mitsubishi Gas Chemical Co., Ltd. Niigata Research Center

Claims (1)

[Claims] 1. A fungicide for agricultural and horticultural use containing at least one of the N-benzyl-N-phenoxyethylammoniu salts shown in Chemical formula 1 as an active ingredient. [Chemical 1] [In the formula, W, X, Y, and Z represent hydrogen, halogen, nitro, or a lower alkyl group having 1 to 4 carbon atoms, and V ⁻ represents halogen, nitric acid, sulfuric acid, phosphoric acid, or acetate ion]