JPS5832854A - Substituted benzanilide derivative and fungicide containing it - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formulaI(R<1> is alkenyl, alkynyl, haloalkenyl, haloalkynyl, haloalkyl, alkoxyalkyl, or alkylthioalkyl; R<2> is methyl or ethyl). EXAMPLE:N-Methyl-3-allyloxy-4'-methoxybenzanilide. USE:A fungicide. Showing improved activity against pathogenic germs of vegetables, especially downy mildew of cucumbers. Also useful as a herbicide for gramineous weeds or broadleaf weeds. Having low toxicity and high safety. PROCESS:A compound shown by the formula II (X is halogen) is reacted with a compound shown by the formula III in a solvent such as acetone, benzene, ether, etc. in the presence of a base (e.g., sodium carbonate, pyridine, etc.) at 0 deg.C- the boiling point of the solvent, to give a compound shown by the formulaI.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel substituted benzanilide derivative and a fungicide containing the same as an active ingredient.

Protecting crops from diseases is extremely important for ensuring stable yields, improving crop quality, and even increasing yields. Various agents such as organometallic compounds and organochlorine compounds have traditionally been used to control plant diseases. There are also many islands that have disadvantages such as pollution. Among these chemicals, there are strong demands for those that cause phytotoxicity to crops and fungicides that have the effect of controlling the emergence of resistant tops.

Until now, the general formula (in the formula, R0' is a hydrogen atom, a lower alkyl group, a 10-gen atom, a trifluoromethyl group, a nitro group, an amine group, a carboxy group, an alkoxycarbonyl group, an allyloxycarbonyl group, a mercapto group, or a hydroxy Methyl group, Y
has the same meaning as R, provided that R1 and Y may be the same or different, but do not mean a hydrogen atom at the same time, n is 1 or 2, X is an oxygen atom or a sulfur atom, and R8 is Residue -N<'', where R4 and R1 are the same or 5 are different; a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, a lower alkyl group or a hydrogen atom, a trifluoromethyl group, It is known that compounds represented by a nitro group, an amine group, an alkoxy group, a phenyl group substituted with a carboxyl group or a hydroxyl group have bactericidal activity (Belgium Patent No. 71435S).
.

In order to further develop compounds with excellent fungicidal effects, the present inventors synthesized various compounds and repeatedly tested their control effects against plant pathogens. The present invention has been completed based on the discovery that the present invention exhibits extremely excellent activity against plant pathogenic fungi, especially downy mildew of cucumbers.

The substituted benzanilide derivative of the present invention has the general formula (wherein R' is an alknyl group, an alkynyl group, a haloalkenyl group, a haloalkynyl group, a haloalkyl group, an alkoxyalkyl group, or an alkylthioalkyl group, and R2 is a methyl group or an ethyl group. (indicates a group). Furthermore, the fungicide of the present invention contains this substituted benzanilide derivative as an active ingredient.

Examples of the substituted benzanilide derivatives of the present invention are shown in Table 1.

Chapter 1 Table CH.

The compound of general formula (Tl) can be produced according to the following reaction formula. In the formula, R1 and R2 have the above-mentioned meanings, and X represents a halogen atom.

The reaction in method (1) is preferably carried out in a solvent in the presence of a base. Examples of solvents include acetone,
Ketone solvents such as methyl ethyl ketone, halogenated hydrocarbons, ethers, petroleum solvents, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, or water are used. As the base, bases commonly used as dehalogenation log agents, such as sodium hydrogen carbonate, potassium carbonate,
Pyridine, triethylamine, dimethylaniline, sodium hydroxide, potassium hydroxide, etc. are used. The reaction can be carried out at any temperature within the range of 0° C. to the boiling point of the solvent, but it is generally sufficient to slightly heat the reaction to quickly complete the reaction.

The reactions in methods (2) and (3) are also preferably carried out in a solvent in the presence of a base. Examples of solvents include alcohol solvents such as evaporated methanol and ethanol, ketone solvents such as acetone and methyl ethyl ketone, halogenated hydrocarbons, ether solvents, petroleum solvents, amide solvents such as dimethylformamide and dimethylacetamide, benzene, Aromatic hydrocarbon solvents such as toluene and xylene, dimethyl sulfoxide, or water are used. As the base, Baka sodium methylate, which is the same as in method (1),
Sodium ethylate, potassium butylade, sodium hydride, etc. are also used. The reaction temperature can be freely selected within the range of 0°C to the boiling point of the solvent, but in general, a temperature range of room temperature to 100°C is preferred in order to quickly complete the reaction.

The reaction in method (4) is also preferably carried out in a solvent such as benzene, toluene, xylene, dimethylformamide, dimethylacetamide, dioxane, etc., in the presence of an alkali hydride. As the alcoholade, for example, sodium methylate, sodium ethylate, potassium butylate, etc. are used, and as the alkali hydride, for example, sodium hydride is used.

The reaction temperature may range from 0°C to the boiling point of the solvent, but preferably from room temperature to 100°C.

Next, a synthesis example will be given and specifically explained.

Synthesis example 1. [Synthesis of N-methyl-3-allyloxy-4'-methoxypenzanilide (compound 1)] 4-methoxy-N-methylaniline 6.99 (0,1
15 mole and 4.2.10.05 mol of sodium bicarbonate) were added to 1 x g of acetone IO, and without stirring, 3-
Allyloxybenzoyl chloride 9.8.9 (0,05
mol) in 30 ml of acetone is added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours to complete the reaction. The reaction mixture is then poured into water and the precipitated oil is extracted with benzene. This extract was washed with water and then dried over anhydrous sodium sulfate, the benzene was concentrated, and the residue was distilled under reduced pressure to obtain N-methyl-3- Allyloxy-4'
-Methoxybenzanilide 13.8I is obtained. The yield is 92.6%.

Synthesis example 2 (N-methyl-3-(2-chloroethoxy)
-4/-Methoxybenzanilide (Synthesis 12)] N-Methyl-3-(2-chloroethoxy)-4-hydroxybenzanilide 15.3.9 (0.05 mo/L/)
% potassium carbonate 7.6.9 (0.055 mol) and methyl iodide 8.59 (0.06 mol) in ethanol 1[
10- Add to the solution and stir under heating and reflux for 3 hours to react. After allowing the reaction mixture to cool, it is poured into water, and the precipitated oil is extracted with benzene. This extract was washed with water, dried with anhydrous sulfuric acid, concentrated with benzene, and the residue was distilled under reduced pressure.
N-methyl-3-(2
-'chloroethoxy) 4/-methoxybenzanilide 14.4 g are obtained. Yield is 90%.

Synthesis Example 3 [Synthesis of N-methyl-4'-methoxy-3-propargyloxybenzanilide (compound 4)] 3.1 g (0,055 mol) of potassium hydroxide was dissolved in 100 mt of ethanol, and N-methyl -3-Hydroxy-4'-methoxybenzanilide 12.9g (0
, 05 mol). While stirring this solution, propargyl bromide 7, II! (0,0?S mol) is added dropwise.

After completion of the dropwise addition, the mixture was stirred for 3 hours under heating and reflux to react.

After cooling, the reaction mixture was poured into water, and the precipitated oil was extracted with benzene. After washing this extract with water, it was dried over anhydrous sodium sulfate, the benzene was concentrated, and the residue was distilled under reduced pressure.
N-methyl-4″ as a pale yellow transparent viscous liquid with 1Hg
13.5 g of -methoxy-3-prono(rugyloxybenzanilide) are obtained. The yield is 912%.

Synthesis Example 4 [Synthesis of N-methyl-4'-methoxy-3-methoxymethoxybenzanilide (compound 6)] 4'-methoxy-3-methoxymethoxybenzanilide IJ
)" 14.4.9 (0.05 mol) was dissolved in dimethylacetamide 100IRt, and sodium hydride 1
．． Add 2 g (0.05 mol) and stir at room temperature for 30 minutes.

8.5 g (1.06 mol) of methyl iodide is added to this and stirred at room temperature for 2 hours to react. After the reaction is complete, the reaction mixture is poured into water and the precipitated oil is extracted with benzene. After washing this extract with water and drying it with anhydrous sodium sulfate, concentrating the benzene and distilling the residue under reduced pressure, a colorless transparent viscous liquid with a boiling point of 158 to 160°C and a boiling point of , N-methyl-4'-methoxy-3-
Methoxymethoxybenzanilide 13.3.9' is obtained. Yield is 88.1%.

Other compounds can also be synthesized according to Synthesis Examples 1 to 4.

The compound of the present invention is a novel benzanilide compound having ether bonds in two aromatic rings, and has a significantly superior control effect on cucumber downy mildew compared to this known compound. In other words, the compound of the present invention has both preventive and therapeutic effects against downy mildew of cucumbers, has excellent permeability through the roots, has characteristics not found in conventional drugs, and is stable. It shows the pest control effect. Furthermore, it has extremely low toxicity to wet animals and fish (and very little residue in crops and the environment), making it excellent in terms of safety.

Furthermore, the compound of the present invention also has an excellent control effect on grass weeds and broad-leaved weeds such as Japanese millet, Japanese millet, Japanese cyperus, Japanese cyperus, and Japanese cyperus, which occur in rice fields.

Next, the fungicide of the present invention has one or more types of general formula (I
), and the compound of the present invention may be used as is, but it is usually blended with carriers, surfactants, dispersants, adjuvants, etc. that are commonly used in the formulation of agricultural chemicals. Then, it is formulated into a powder, a wettable powder, an emulsion, a fine granule, or a granule using a conventional method.

Suitable carriers include, for example, solid carriers such as Merck, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea, or liquid carriers such as isopropyl alcohol, xylene, and cyclohexanone. Examples of surfactants and dispersants include alcohol sulfate salts, alkyl sulfonate salts, diallylalkyl disulfonate salts, lignin sulfonate salts, polyoxyethylene glycol ether, polyoxyethylene alkyl allyl ether, and polyoxyethylene sorbitan monoalkaline salts. Examples include chelates and the like. Examples of the adjuvant include carboxymethyl cellulose, polyethylene glycol, gum arabic, and the like. These preparations can be diluted to an appropriate concentration and sprayed or applied directly.

The fungicide of the present invention can be mixed with or used in combination with other fungicides, plant growth regulators, fertilizers, and the like.

The amount of the fungicide of the present invention to be used is 10 ares and 10[1 to
It is 500g. In the case of a liquid preparation, it is preferable to dilute the active ingredient to a concentration of 100 to 11,000 pp.

Next, formulation examples will be given and specifically explained. The numbers in the formulation examples indicate weight.

Formulation Example 1 (Powder) A mixture of 2% compound (1), 5% diatomaceous earth, and 96% clay is uniformly mixed and pulverized to obtain a powder.

Formulation Example 2 (Aqueous phase agent) Compounds (4150%, diatomaceous earth 45%, sodium dinafuculmethane disulfonate 2%, and lignin sulfonic acid) 6% IJum were uniformly mixed and ground to prepare an aqueous phase agent.

Formulation Example 3 (Emulsion) Compound α→30%, cyclohexanone 20%, polyoxyethylene alkyl allyl ether 11%, calcium alkylbenzenesulfonate 4'! and 35% of methylnaphthalene were uniformly dissolved to form an emulsion.

Formulation example (4) (granules) Compound 065%, sodium salt of lauryl alcohol sulfate 2%, sodium lignin sulfonate 5%,
2% carboxymethylcellulose and 86 parts of clay are uniformly mixed and ground. To this mixture, 20 parts of water is added and kneaded, processed into granules of 14 to 32 mesh using an extrusion type granulator, and then dried to form granules.

Next, the effects of the compounds of the present invention on cucumber downy mildew will be explained using test examples. In addition, the following were used as comparative compounds and comparative drugs in the test examples.

OC1-r.

l OCR.

Comparative drug: Daconil (commercially available fungicide containing tetrachloroisophthalonitrile as an active ingredient) Test Example 1 (Preventive effect test against cucumber downy mildew) ゛ - 15 cucumbers per pot were grown in an inner pot with a side of 9 cm (variety: When the plants (Sumo Hanpaku) reached the futaba stage, the aqueous phase agent prepared according to Formulation Example 2 was diluted with water to a predetermined concentration and sprayed at 30 IRt per two pots using a spray gun. After the spray solution is air-dried, a conidial suspension of cucumber downy mildew fungi (
Spore count I x 10'c/ml) per pot
It was inoculated by spraying. The plants were then kept in a greenhouse at 21° C. for 24 hours and then transferred to a greenhouse, and 8 days after inoculation, the disease state was investigated according to the following criteria.

The results are shown in Table 2. The disease severity was calculated as follows.

Disease index 0: Leaves with no lesions 1: Leaves where the diseased area is less than H of the leaf area Disease index 2: Leaves where the diseased area is greater than or equal to % of the leaf area and less than % 3: Leaves that are more than % of the leaf area Table 2 Test Example 2 ( Treatment effect test for cucumber habit) 15 cucumbers were grown per pot in an inner pot with a side of 9 cR (
Cultivar: Sumo Hanpaku) was injected with 1 conidial suspension of cucumber downy mildew fungus (number of spores 1 x 10'/ml) when it was in the bile stage.
2 tnl was sprayed per pot and kept in a 21°C chamber for 24 hours. Next, the hydrating powder prepared according to Formulation Example 2 was diluted with water to a predetermined concentration, and sprayed with a spray gun to give 3 ml per 2 pots.
0m/sprayed. The sprayers were placed in a greenhouse and investigated in the same manner as in Example 1 of the ridge pressure test 8 days after inoculation. The results are shown in Table 3.

19-3 Table 90- Test Example 3 (Cucumber downy mildew control effect test by penetration transfer from roots) An inner pot with a side of 9α was filled with river sand, and cucumber seeds (variety:
Sumo Hanpaku) was sown at 10 seeds per pot, and when it reached the futaba stage, a wettable powder prepared according to Formulation Example 2 was diluted with water to a specified concentration, poured 24 ml per pot, and then placed in a greenhouse for 3 days. Place it inside;
Conidial suspension of cucumber downy mildew fungus (number of spores l x 10'
2 sprays/wIt) per pot. After keeping it in a greenhouse at 21℃ for 24 hours, it was transferred to a greenhouse, and 8 days after inoculation,
The investigation was conducted in the same manner as Test Example 1. The results are shown in Table 4.

Table 4 patent applicant Kumiai Chemical Industry Co., Ltd. President and Director Mozuki Itobu

Claims (1)

[Claims] 1. General formula (11j/ in the formula represents an alkenyl group, an alkynyl group, a haloalkenyl group, a haloalkynyl group, a haloalkyl group, an alkoxyalkyl group, or an alkylthioalkyl group)
2 represents a methyl group or an ethyl group. ) A substituted benzanilide derivative represented by 2. General formula (in the formula, R/ is an alkenyl group, an alkynyl group, a haloalkenyl group, a haloalkynyl group, a haloalkyl group, an alkoxyalkyl group, or an alkylthioalkyl group, and W is
Indicates a methyl group or an ethyl group. ) A bactericide characterized by containing a substituted benzanilide derivative represented by the following as an active ingredient.