JPH0331702B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the following formula: {In the formula, R ₁ represents an alkyl group having 1 to 3 carbon atoms or a halogen atom, R ₂ represents -NO ₂ or -NH ₂ , and R ₃ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, represents a group or a halogen atom, R ₄ is a hydrogen atom or has 1 to 3 carbon atoms
R ₅ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (However, the two ortho positions of the aniline part of the molecule are always substituted.) R ₈ represents the number of carbon atoms. 1 to 3 alkyl groups, B represents the following formula: -CH ₂ Z [wherein, Z represents the following formula: -X-R ₁₃ (wherein, X represents an oxygen atom or a sulfur atom, and R ₁₃ is represents a group represented by ) represents an alkyl group having up to 4 carbon atoms; }. Therefore, the present invention provides substituents on the aniline ring.
These compounds include aniline derivatives having R ₂ , R ₃ , R ₄ and R ₅ , each of whose substituents can be in the 3, 4, 5 or 6 position; Positions (=2, 6) are always substituted. Depending on the number of carbon atoms given, an alkyl group can be used as such or as part of other substituents, for example the following groups: methyl, ethyl, propyl or butyl and their isomers, for example isopropyl. group, isobutyl group, sec-butyl group or tertiary-butyl group. As used herein, the term "halogen" refers to a fluorine atom, a base atom, a bromine atom or an iodine atom, preferably a chlorine atom or a bromine atom. The compound represented by the formula is a resinous or solid substance which is stable in air at room temperature and has a very useful microbicidal action. The compounds are ideally suited for controlling harmful microorganisms, especially for suppressing or killing fungi, primarily in agriculture. Particularly preferred compounds are those represented by the formula having a substituent R ₂ at the 3-position of the molecule. Substituted acylaniline derivatives have already been used as microbicides, for example in German Patent Publication No.
No. 2643477, No. 2741437, No. 2513788, No.
Proposed in No. 2513732, No. 2515091 or No. 2927461. However, these known microbicides often have a number of drawbacks. These disadvantages include the difficulty of application due to the physico-chemical properties of the material and the power of penetration or adhesion to the plants desired to be protected. In fact, foliar fungicides are usually sprayed onto the plant and microdispersed onto the surface. In this state the disinfectant is exposed to the action of weather conditions, such as rain, wind, sunlight and temperature. Therefore, before a fungicide can exhibit sufficient action, its active ingredients are often dispersed from the plant body due to, for example, undesirable high water solubility, low photostability, high volatilization, etc. It has proven extremely difficult to find highly effective microbicides that do not exhibit these physico-chemical disadvantages. Therefore, at very low concentrations, significant bactericidal action,
There is indeed an urgent need for fungicides which can also stick to plants for a sufficient period of time. Surprisingly, the inventors have found that the new compound represented by the formula simultaneously possesses many excellent properties according to the practical requirements. Not only do they have a useful microbicidal spectrum against important or harmful fungi, but they also have application advantages. Due to its remarkable low water solubility and very low vapor pressure, it maintains contact with plants for a considerably longer period of time, so that it exerts its bactericidal action more easily and less sensitive to weather conditions. Therefore, the compounds of the formula can be used much more effectively in practice than comparable compounds of the prior art. Bactericidal compounds represented by the formula having the following substituents or combinations thereof are preferred; _R1 : methyl group, halogen atom, _R2 : _-NO2 , _-NH2 , _R3 : hydrogen atom, methyl group , halogen atom, R ₄ , R ₅ : hydrogen atom, methyl group, R ₈ : alkyl group having 1 to 3 carbon atoms, B: -CH ₂ O (alkyl group having 1 to 3 carbon atoms), range of the formula More preferred aniline derivatives within, for example, form a subgroup consisting of compounds having the following types of substituents or combinations thereof: _R1 : methyl group, _R2 : _-NO2 , _-NH2 , R ₃ : Hydrogen atom, methyl group, chlorine atom, bromine atom, R ₄ , R ₅ : Hydrogen atom, methyl group, R ₈ : Methyl group, isopropyl group, B: -CH ₂ O (having 1 to 3 carbon atoms) alkyl group), the following individual compounds are particularly preferred due to their pronounced action against phytopathogenic microorganisms: N-(1'-methoxycarbonylethyl)-N-methoxyacetyl-2-methyl-6-aminoaniline, N -(1'-methoxycarbonylethyl)-N-methoxyacetyl-2-methyl-6-nitroaniline, N-(1'-methoxycarbonylethyl)-N-methoxyacetyl-2,6-dimethyl-3-nitroaniline , N-(1'-methoxycarbonylethyl)-N-ethoxyacetyl-2,6-dimethyl-3-nitroaniline, N-(1'-isopropyloxycarbonylethyl)-N-methoxyacetyl-2,6-dimethyl -3-nitroaniline, N-(1'-methoxycarbonylethyl)-N-methoxyacetyl-2,6-dimethyl-3-aminoaniline, N-(1'-methoxycarbonylethyl)-N-methoxyacetyl-2 , 3-dimethyl-6-aminoaniline and N-(1'-methoxycarbonylethyl)-N-methoxyacetyl-2,3-dimethyl-6-nitroaniline, depending on the type of substitution, the compounds represented by the following formulas are: As shown in A to E and G, it can be obtained by various methods. In formulas a, b, and, substituents R ₁ to
R ₅ , R ₈ , R ₁₃ , X and B have the meanings defined in the formula. Y is a customary free radical, such as a benzenesulfonyloxy group, p-bromobenzenesulfonyloxy group, p-tosyloxy group, trifluoroacetyloxy group, lower alkylsulfonyloxy group, such as mesyloxy group, or in particular a halogen atom, For example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Hal is
It represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, especially a chlorine atom or a bromine atom. The individual steps to be carried out according to the method of the invention are as shown below: The compound of the formula A. The compound represented by the formula is converted into the following reaction formula: B. By acylation with a carboxylic acid represented by the formula or a reactive derivative thereof, as shown in the following reaction formula: (wherein Y represents a conventional leaving group) or by reacting a compound represented by formula C. with a compound represented by formula C. as shown in the following reaction scheme: D. By nitration with a reactive nitrating agent to obtain a compound of formula (the compound obtained in this manner is referred to herein and below as a), or D. a compound of subgroup a, Reaction formula below: By hydrogenation with a customary hydrogenating agent to obtain the compounds of the formula herein and hereinafter referred to as b, as shown in E.
In order to obtain one representing the CH ₂ XR ₁₃ group, the compound represented by the formula is converted into or by reacting the compound represented by the formula G. with the compound represented by the following reaction formula: (In the formula, R' represents a hydrogen atom or a hydrocarbon group.) As shown in the formula, it can be produced by esterification or transesterification with a compound represented by the formula in the presence of a strong acid. In the above variants A to E and G, substituents R ₁ to R ₅ , R ₈ , R ₁₃ , X and B in formulas a, b, to and have the meanings defined in the formulas, and M is hydrogen. represents an atom or a metal cation and Hal represents a halogen atom. Most of the starting materials are known or obtained by methods known per se. The starting compounds of the formula, and can be prepared, for example, in a manner analogous to that described in variants C and D, ie by nitrating the aniline derivatives and optionally subsequently hydrogenating them. can. The above modified method is preferably carried out under the following reaction conditions. Variant A: In this variant, reactive derivatives of the compounds of the formula, such as acid halides, acid anhydrides or esters, can be advantageously used. Among these, acid chlorides and bromides are particularly suitable. The reaction temperature ranges from 0° to 180°C, with a preferred range from 0° to 150°C or the boiling point of the solvent or solvent mixture. In some cases, acid acceptors or condensing agents, such as organic and inorganic bases, such as tertiary amines such as trialkylamines (trimethylamine, triethylamine, tripropylamine, etc.), pyridine and pyridine bases (4-dimethylamine), etc. pyridine, 4-pyrrolidyl-aminopyridine, etc.), alkali metal and alkaline earth metal oxides and hydroxides,
Preference is given to using carbonates and hydrogencarbonates and alkali acetates. Also, the hydrogen halide formed is in some cases removed from the reaction mixture by introducing an inert gas, for example nitrogen gas. N-
Acylation can be carried out using inert solvents or diluents, such as aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, petroleum ether; halogenated hydrocarbons, such as chlorobenzene,
Methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ethers and ether compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, etc.), anisole,
Dioxane, tetrahydrofuran; Nitriles, such as acetonitrile, propionitrile;
It can be carried out in the presence of N,N-dialkylated amides such as dimethylformamide; dimethylsulfoxide; ketones such as acetone, diethyl ketone, methyl ethyl ketone; mixtures of these solvents. In some cases, the acylating agent itself can be used as a solvent. The presence of a reaction catalyst, such as dimethylformamide, is advantageous for the acylation. Variant B: In this variant, the substituent Y in the formula is a conventional leaving group, for example a benzenesulfonyloxy group, a p-promobenzenesulfonyloxy group,
a p-tosyloxy group, a trifluoroacetyloxy group, a lower alkylsulfonyloxy group, such as a mesyloxy group, or especially a halogen atom,
For example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom or a bromine atom. In this variant, the starting compound of the formula is first converted to the corresponding alkali salt with butyllithium, sodium hydride or an alkali carbonate (e.g. sodium carbonate), or in the presence of an acid acceptor, the variant It is convenient to carry out the reaction in the same temperature range as in A, preferably with the addition of a catalytic amount of alkali iodide. Variant C Suitable nitrating agents in this variant are active nitrating agents, ie any substances capable of liberating nitronium ions NO ₂ ⁺ . Therefore, besides nitric and nitrating acids (1HNO ₃ :2H ₂ SO ₄ ), organic nitrates such as acyl nitrates (acetyl nitrate) can be used as nitrating agents in convenient formulations (e.g. glacial acetic acid/acetic anhydride/ 65-100% _HNO3 ). To increase the reaction rate,
It is possible to warm the reaction mixture, but increasing the temperature too quickly is not a good idea because nitrous gas is evolved. Variant D: For the hydrogenation of the nitro group, in addition to the customary inert organic solvents, in particular lower alkanols, e.g.
Methanol, ethanol or isopropanol can be used. Suitable solvents are also aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, petroleum ethers; ethers and ether compounds, such as dialkyl ethers (diisopropyl ether, tert-butyl methyl ether, etc.), anisole, dioxane, Tetrahydrofuran; dimethyl sulfoxide; or esters such as ethyl acetate, propyl acetate, etc. When the starting material of formula a is a liquid, the hydrogenation can also be carried out without a solvent.
Furthermore, the hydrogenation can also be carried out in multiphase systems, for example in toluene/H ₂ O or xylene/H ₂ O and in glacial acetic acid. Hydrogenation can be carried out in a wide variety of ways. Besides the customary means using nascent hydrogen (base metal in acid solution), electrolysis or means with reducing agents such as alkali hydrides or lithium aluminum hydride, catalytic hydrogenation are particularly suitable. Suitable hydrogenation catalysts are black catalysts (very finely divided metal precipitates, e.g. metals or noble metals precipitated from solutions of their salts by reduction), e.g. platinum, palladium or nickel: noble metal oxides, e.g. Platinum oxide (); skeletal catalyst consisting of a suspension of binary alloys, e.g.
Runny Nickel; supported catalyst consisting of a black catalyst deposited on the surface of a support material, e.g. charcoal, silica, alumina, alkaline earth metal sulfates and carbonates; oxide and sulfide catalysts, e.g. copper chromite, zinc These include zinc chromate, molybdenum sulfide, and tungsten sulfide. The hydrogenation is preferably carried out at normal pressure or at a pressure below 20 bar, during which the reaction mixture is heated between 0° and
Maintained in the range of 150℃. Other than the above catalysts,
For example, when using iron, chromium, cobalt or copper, higher altitudes and higher pressures are required for hydrogenation. Variant E: When M represents a hydrogen atom, it is advantageous to use salt-forming agents, such as oxides, hydroxides or hydrides of alkali metals or alkaline earth metals. Variant G: The reaction is catalytically influenced by acids and bases. The process is carried out with an excess of HOR ₈ in order to shift the equilibrium in the desired direction.
R′ and R ₈ represent different meanings. R' represents a hydrogen atom or a hydrocarbon group, in particular hydrogen or a lower alkyl group, such as a methyl group or an ethyl group. In all process variants, anhydrous organic solvent and/or
Alternatively, it is advantageous to use organic solvents saturated with inert gases. Carrying out the process in an inert gas atmosphere, for example under _N2 , can have a favorable influence on the reaction process. If no specific solvent is mentioned in Process Variants A to E and G, generally any solvent that is inert to the reactants may be used. Examples of such solvents include: aliphatic and aromatic hydrocarbons, e.g.
benzene, toluene, xylene, petroleum ether,
Halogenated hydrocarbons, e.g. chlorobenzene, methylene chloride, ethylene chloride, chloroform: ethers and ether compounds, e.g.
Dialkyl ethers, dioxane, tetrahydrofuran; Nitriles, such as acetonitrile;
N,N-dialkylated amides such as dimethylformamide: dimethylsulfoxide; ketones such as methyl ethyl ketone; mixtures of such solvents. In the above methods, it is usually not necessary to isolate intermediates. Moreover, the method can be carried out continuously in the same reaction vessel. The process for preparing the compounds of the formula, including all substeps (variants A to E and G), also constitutes an object of the invention. The compounds of the formula have a non-binding carbon atom in the side chain adjacent to the COOR ₈ group and can be separated into their optical antipodes by conventional means. That is, for example, by fractionally crystallizing a salt of the compound represented by the above separation formula with an optically active acid, and then reacting the optically pure compound to obtain a compound, or by obtaining an optically active base. and the free acid (R'=H), and then reacting the optically pure compound to obtain the compound. The optical antipodes of the compounds of formula have different microbicidal properties. Depending on the mode of substitution, other non-satile carbon atoms may be present in the molecule. Irrespective of the optical isomerism described above, when the phenyl ring is substituted asymmetrically with respect to the phenyl-IN< axis, atropisomerism is observed at the axis portion. Unless the synthesis is carried out with the aim of isolating the pure isomer, the compounds of the formula will usually be obtained as a mixture of possible isomers. Surprisingly, the inventors have found that the compounds of the formula have a very useful microbicidal spectrum depending on the application. These compounds can be used, for example, to protect cultivated plants. The main fields of use of the compound represented by the formula are:
The purpose is to control harmful microorganisms, especially plant pathogenic bacteria. These compounds therefore have a very useful therapeutic and prophylactic action for protecting cultivated plants without adversely affecting them through undesired side effects. Examples of cultivated plants within the scope of the invention include: Cereals (wheat, barley,
rye, oats, rice); beets (sugar beets and forage beets); pears, stone fruits and soft fruits (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, black strawberries); legumes ( oil plants (oil, mustard, poppy, olive, sunflower, coconut, castor, cocoa and peanut); cucurbits (currant, pumpkin and melon) ; fiber plants (cotton, flax, hemp, jute); citrus fruits (oranges, lemons, grapefruit, tangerines); vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, and bell peppers); or Examples include plants such as corn, tobacco, nuts, coffee, sugar cane, tea plants, vines, hops, bananas and natural rubber plants, as well as ornamental plants. Whole plants or plant parts (fruits, seeds, leaves, stems, tubers or roots) of these crops and related crops
The compound of the formula inhibits or kills microorganisms that occur in plants and also protects subsequently growing parts of the plant from such microorganisms. The compound represented by the formula is effective against plant pathogenic fungi belonging to the following types: Oomycetes belonging to the Phycomycetes, such as Peronosporales (Phytophthora, Pythium, Plasmopara), and Ascomycetes, such as Peronosporales Erysiphe and Venturia. In addition, the compounds of the formula have systemic action and can also be used as dressing agents to protect seeds (fruits, tubers, grains) and cuttings from fungal infections and from microorganisms occurring in the soil. can. The invention therefore also relates to the use of the compounds of the formula for the control of phytopathogenic microorganisms and for the protective treatment of plants, in order to protect them from attack by phytopathogenic microorganisms. The compounds of the formula can also be applied simultaneously or sequentially with further compounds to the area or plants to be treated. Such other compounds may be fertilizers or micronutrient donors, or other formulations that influence plant growth. These are also selective herbicides, insecticides, fungicides, bactericides,
It may be a nematicide, a molluscicide or a mixture of some of the formulations, optionally with other carriers, surfactants or application-enhancing aids used in conventional formulation techniques. Suitable carriers and auxiliaries may be solid or liquid and correspond to the substances customary in formulation technology, such as natural or recycled mineral substances, solvents, dispersants, wetting agents, adhesives, binders or fertilizers. Surfactants in this case mean surface-active or surface-active compounds that are normally dissolved or dispersed in liquids and are selectively adsorbed at interfaces. The surfactant molecule contains at least one group with an affinity for strongly polar substances - thereby providing solubility in water, and at least one other group with an incompatibility towards water. do. Therefore, surfactants are hydrophobic [i.e. lipophil]
moieties, usually hydrocarbon groups having alkyl and/or aryl moieties, and also molecules having hydrophilic [ie, non-lipophilic] moieties, such as perfluoroalkyl groups. Products used in practice are often mixtures of such compounds. Surfactants not only disperse the active ingredient uniformly in a liquid, e.g. aqueous medium, but also
It also has the effect of increasing the wetness of the plants: this leads to a reduction of the proportion of active ingredient in the ready-to-use formulation and thereby to a lower level of environmental pollution. The content of active ingredients in commercially available compositions ranges from 0.01 to
90% by weight, the amount of auxiliaries is 10 to 99.99% by weight, and the proportion of surfactants among the auxiliaries is generally 0 to 30% by weight. The present invention also provides a composition containing a compound represented by the formula as at least one active ingredient,
and the use of said compositions for inhibiting and/or preventing attack by microorganisms. Furthermore, the invention relates to the preparation of said compositions, which consist in homogeneously mixing the active ingredient with one or more of the substances or groups of substances mentioned above. The present invention further relates to a method for controlling microorganisms using a compound represented by the formula or a composition containing the compound. The present invention will be explained in more detail with reference to the following examples, but no limitations are intended by this description. Parts and percentages are by weight. Unless otherwise specified, compounds represented by the formula are mixtures of isomers. Example 1: The following formula: Production of N-(1'-methoxycarbonylethyl)-N-ethoxyacetyl-2,6-dimethyl-3-nitroaniline represented by Anhydrous tetrahydrofuran saturated with nitrogen gas
To a solution of 3 g of 55% sodium hydride in 70 ml at room temperature, while stirring and simultaneously introducing nitrogen gas, 16 g of N-ethoxyacetyl-2,6-dimethyl-3-nitroaniline was dissolved in 30 ml of the same solvent.
Add dropwise a solution of . After the slightly exothermic reaction had subsided, the mixture was heated to 55°C and methyl 2-bromopropionate was dissolved in 20 ml of tetrahydrofuran.
Add a solution containing 12.7 g. During the addition the temperature rises to 60°C. The mixture was stirred at 55 °C for 12 h, then cooled to room temperature and poured into 100 ml of water.
Extract twice with 100 ml of ethyl acetate each time. The combined extracts were washed with water, dried with sodium sulfate,
Excess solvent is removed under reduced pressure. The oily crude product is purified by column chromatography on silica gel using a 1:1 mixture of chloroform/diethyl ether as eluent. Fractions 5-30 are collected and the solvent is removed under reduced pressure.
Compound 31 is obtained as a viscous oil with a refractive index n ²⁴ _D =1.5325. Example 2: The following formula: N-(1'-methoxycarbonylethyl)-N-methoxyacetyl-2-amino-6-
Preparation of methyl-aniline 257.4 g of N-(1'-methoxycarbonylethyl)-N-methoxyacetyl-2-methyl-6-nitroaniline was dissolved in 2.6 g of absolute methanol, and the solution was heated at 20°-25°C and , Runny Nickel under normal pressure
Hydrogenate for 26 h in the presence of 26 g (absorption of H ₂ :
56.2 = 100% of theoretical value). The catalyst is then removed by filtration, the liquor is concentrated and the oily residue is crystallized by addition of diethyl ether. Yield: 170.8 g of a compound with a melting point of 86°-88°C. Example 3: The following formula: Production of N-(1'-methoxycarbonylethyl)-N-methoxyacetyl-2,6-dimethyl-3-nitro-aniline represented by
Add dropwise to 32 g of (1'-methoxycarbonylethyl)-2,6-dimethyl-3-nitroaniline at room temperature. After the slightly exothermic reaction subsided, the reaction solution was stirred at room temperature for 20 hours. The solvent is then removed and the dark red oily residue is distilled under high vacuum. Compound 28 is
It distills out as a pale yellow oil at a temperature of 170°-174°C and a pressure of 0.07 mbar. The following compounds of the formula are prepared by analogous means:

【table】

【table】

Table For application, the compounds of the formula can be processed into the following dosage forms: Formulation Examples Example 7 Solid formulations: Powders and dispersions generally contain less than 10% of the active ingredient. A 5% powder consists of, for example, 5 parts of active ingredient and an auxiliary agent, such as 95 parts of talc; a 2% powder consists of 2 parts of active ingredient, 1 part of highly dispersed silica and 97 parts of talc. Mixtures of these with other carriers and auxiliaries customary in compounding technology are also possible. These powders and dispersions are prepared by mixing and milling the active ingredient with the carrier and auxiliaries and can be applied in this form by dusting. Granules: for example coated, impregnated and homogeneous granules and pellet granules usually contain from 1 to 80% of active ingredient. Therefore, a 5% granule may contain, for example, 5 parts of active ingredient, 0.25 part of epoxidized vegetable oil,
It consists of 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol and 91 parts of kaolin (preferred particle size: 0.3-0.8 mm). The granules are
It can be prepared as follows: the active ingredient is mixed with vegetable oil, the mixture is dissolved in 6 parts of acetone and polyethylene glycol and cetyl polyglycol ether are added. The resulting solution is sprayed onto kaolin and the acetone is subsequently evaporated off under reduced pressure. This type of fine granules is conveniently used to control fungi in soil. Example 8: Liquid formulations: Generally divided into active ingredient concentrates that can be dispersed or dissolved in water and aerosols. Active ingredient concentrates that can be dispersed in water include, for example, wettable powders and pastes;
These usually contain 25-90% of the active ingredient in commercially available packs.
%, 0.01 of active ingredient in ready-to-use solution
Contains 15% to 15%. Emulsifiable concentrates contain active ingredients
10 to 50%; liquid concentrates contain 0.001 to 20% of the active ingredient in ready-to-use solution. Therefore, a 70% hydrating agent contains, for example, 70 parts of the active ingredient, 5 parts of sodium dibutylnaphthalene sulfonate, and a naphthalene sulfonic acid/phenolsulfonic acid/formaldehyde condensate (mixing ratio: 3:
2:1), 10 parts of kaolin and 12 parts of chiyoke, e.g. 40%
Hydrating agents include, for example, the following substances: 40 active ingredients
part, sodium lignosulfonate 5 parts, sodium dibutylnaphthalene sulfonate 1 part and silicic acid
Consists of 54 parts. 25% hydrating powders can be prepared in a variety of ways. For example, 25 parts of active ingredient, 4.5 parts of calcium lignosulfonate, Chiyok, for example,
1.9 parts of a mixture of Xyanpentyoke/hydroxyethylene cellulose (1:1), 1.5 parts of sodium dibutylnaphthalene sulfonate, 19.5 parts of silicic acid,
It may consist of 19.5 parts of cypress yoke and 28.1 parts of kaolin. In addition, a 25% hydrating agent can be prepared using, for example: 25 parts of active ingredient, 2.5 parts of isooctylphenoxy-polyoxy-ethylene-ethanol, 1.7 parts of a mixture of cyanopentyoke/hydroxyethylcellulose (1:1), and 8.3 parts of sodium silicate. , 16.5 parts diatomaceous earth and 46 parts kaolin. A 10% hydrating agent, for example, contains 10 parts of active ingredient,
It consists of 3 parts of a mixture of sodium salts of saturated fatty alcohol sulfonates, 5 parts of a naphthalene sulfonic acid/formaldehyde condensate and 82 parts of kaolin. Other hydrating agents contain 5 to 30 parts of active ingredient, e.g.
It is a mixture of 5 parts of an adsorbent carrier such as silicic acid and 55 to 80 parts of a carrier such as kaolin with a dispersant mixture consisting of 5 parts of sodium arylsulfonate and 5 parts of alkylaryl polyglycol ether. A 25% emulsion concentrate is e.g.
It contains the following emulsifying substances: 25 parts of active ingredient, 2.5 parts of epoxidized vegetable oil, 10 parts of alkylaryl sulfonate/fatty alcohol polyglycol ether mixture, 5 parts of dimethylformamide and 57.5 parts of xylene. Emulsions of the desired application concentration are prepared by diluting concentrates of the type described above with water; these emulsions are particularly suitable for foliar application. Furthermore, other hydrating powders containing different mixing ratios or other additives and carriers customary in formulation technology can be prepared. The active ingredient is homogeneously mixed with the above additives using suitable mixing equipment and the mixture is then ground in suitable mills and rollers. Wettable powders with excellent wetting and suspending properties are obtained. The wettable powders can be diluted with water to obtain suspensions of the desired concentration, which are particularly suitable for foliar applications. Compositions of this type also constitute an object of the present invention. The compound treated by the above-mentioned method and represented by the formula as an active ingredient (for example, No. 2, 6,
8, 10, 28, 31, 33, 48, 57, 59, 73 or 74)
can be used with very high success in controlling phytopathogenic microorganisms. Also,
Other compounds shown in Tables 1-2 may be used with similar or similar success rates. Biological Test Examples Example 9: Action against powdery mildew (Erysiphe graminis) in barley Residual protective effect Barley plants approximately 8 cm in height were sprayed with a spray mixture obtained from the active ingredient prepared as a hydrating powder (the active ingredient
0.02%) was sprayed. The treated plants are sprayed with conidia of the fungus after 3-4 hours. The infected barley plants were then placed in a greenhouse at approximately 22°C. The bacterial infection status was evaluated 10 days later. A compound represented by the formula, for example, compound No.
Treatment of barley plants against powdery mildew with 10, 104, 107 or 142 reduced fungal infection to less than 10% compared to control plants (100% infection). Example 10: Action against Phytophthora infection of tomato plants a) Residual protective action After 3 weeks of cultivation, tomato plants were sprayed with a spray solution prepared from a wettable powder of the active ingredient (0.06% active ingredient). After 24 hours, the treated plants were infected with a saturated sac suspension of the fungus. The infected plants were incubated for 5 days at 20° C. and a relative humidity of 90 to 100%, and then fungal infection was evaluated. Compound No. 2, 6, 8, 10, 28, compared to untreated control plants (100% infected).
29, 31, 33, 48, 57, 59, 73, 74, 78, 88, 102
Infection of plants treated with any of compounds 107, 141, 142, 158, or 159 was less than 10%. b) Osmotic action A spray prepared from a hydrating powder of the active ingredient (0.06% active ingredient based on the soil volume) was applied to tomato soil that had been cultivated for 3 weeks. Care was taken to avoid contact of the spray with plant parts on the soil. After 48 hours, the treated plants were infected with a sporangial suspension of the fungus. Infected plants were incubated at 90−100% relative humidity and 20°C.
After culturing for 5 days, bacterial infection was evaluated. In the above test, compounds No. 2, 6, 8, 10,
28, 29, 31, 33, 48, 57, 59, 73, 74, 78, 88,
Among the compounds of the present invention, compounds 102 to 107, 141, 142, 158 and 159 exhibited very good penetration effects.
Compared to untreated control plants (100% infection), fungal infection was almost completely inhibited by the compound (0 to 5%). c) Residual therapeutic action After 3 weeks of cultivation, tomato plants were infected with a sporangial suspension of the fungus. Temperature 20℃, relative humidity 90~
After 22 hours of incubation in a humid chamber at 100°, the infected plants were dried and then sprayed with a spray solution prepared from a wettable powder of the active ingredient (0.06% active ingredient). After drying the spray coating, the treated plants were returned to the humidity chamber. Bacterial infection was evaluated on the 5th day after infection. Compared to untreated and infected control plants (100% infected), compounds No. 2, 6, 8, 10, 28, 29, 31,
Infection of plants treated with any of 33, 48, 59, 74, 107, 141 and 142 was less than 10%. Example 11 Venturia scab fungus on apple branches
residual protective effect against apple young branches cut into 10-20 cm lengths.
A spray solution obtained from a wettable powder of the active ingredient was sprayed. After 24 hours, the treated plants were infected with a conidial suspension of the fungus. Next, the plants were placed at a relative humidity of 90-
The cells were cultured at 100% for 5 days and placed in a greenhouse for an additional 10 days at 20°-24°C. On day 15 post-infection, lesion development was assessed. Compounds No. 8, 10, 28 and 31 inhibited infection by 10
Reduced to -15%. Example 12: Pythlum blight disease fungus of sugar beet plants
a) Effect after soil application The fungus was cultivated in a culture solution of carrot pieces and then added to the soil and sand mixture. The soil infected using this method was placed in flower pots and sugar beet seeds were sown. Immediately after sowing, a test preparation prepared from a wettable powder (20 ppm of active ingredient based on the soil volume) was poured onto the soil. The flower pots were then kept in a greenhouse at 20-24°C for 2-3 weeks. The soil was kept evenly moist during this period by light watering. As an evaluation of the test, sugar beet germination and the number of healthy and unhealthy plants were measured. b) Effect after application of seed dressing The fungus was cultivated in a culture solution of carrot pieces and added to the soil and sand mixture. The infected soil was placed in flower pots and sugar beet seeds treated with the test preparation prepared as seed dressing powder (0.06% of any one of the compounds in Tables 1 and 2) were sown. Next, this pot was left in a greenhouse at about 20°C for 2-3 weeks. The soil was watered little by little to keep the humidity constant. Measure the number of germination of sugar beet plants,
The test was evaluated. In both tests, compounds No. 2, 6, 8, 10,
28, 29, 31, 33, 48, 59, 73, 107, 158 and
160 showed sufficient efficacy against seedling damping-off fungi (over 90% of germinated plants). The germinated plants had a healthy appearance. A similarly good effect was also achieved against corn seedling blight disease fungi in a similar test. Example 13: Powdery mildew fungus (Podosphaera) on apple plants
leucotricha) Apple seedlings at the 5-leaf stage were sprayed with a spray solution prepared from a wettable powder of the active ingredient (0.06% active ingredient). After 24 hours, the treated plants were infected with a conidial suspension of the fungus and transferred to a room controlled at 70% relative humidity and 20°. Fungal infection was assessed on day 12 post-infection. Untreated and infected control seedlings (100%
Compound No. 2, 6, 8, 10, 28,
Infection of seedlings treated with 31, 33, 48 or 73
% or less. Example 14 Measurement of physico-chemical data The commercially available fungicide “Metalaxyl” known from US Pat.
xyl)” [N-(2,6-dimethylphenyl)-N-
(2'-Methoxyacetyl)alanine methyl ester], the compounds of the invention have a similar chemical structure but have significantly better physicochemical data for the residual action of fungicides. a) low solubility in water

【table】

[Table] b) Low volatility Evaporation half-life of each disinfectant of the present invention in an evaporation tube
T ₅₀ was measured at 50° C. in an air flow of 20 m/h. The values are shown in the table below in comparison with the corresponding half-life T ₅₀ of metalaxyl.

TABLE The above tests a) and b) demonstrate the physico-chemical advantages of the compounds of the formula. These advantages prevent undesired premature loss of the active ingredient, thereby ensuring long-term efficacy of the composition.

Claims (1)

[Claims] Primary formula: {In the formula, R ₁ represents an alkyl group having 1 to 3 carbon atoms or a halogen atom, R ₂ represents -NO ₂ or -NH ₂ , and R ₃ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, represents a group or a halogen atom, R ₄ is a hydrogen atom or has 1 to 3 carbon atoms
R ₅ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (However, the two ortho positions of the aniline part of the molecule are always substituted.) R ₈ represents the number of carbon atoms. 1 to 3 alkyl groups, B represents the following formula: -CH ₂ Z [wherein, Z represents the following formula: -X-R ₁₃ (wherein, X represents an oxygen atom or a sulfur atom, and R ₁₃ is represents a group represented by ) represents an alkyl group having up to 4 carbon atoms; } A compound represented by. 2 R ₁ represents a methyl group or a halogen atom, R ₂ represents NO ₂ or NH ₂ , R ₃ represents a hydrogen atom, a methyl group or a halogen atom, and R ₄ and R ₅ are independently each represents a hydrogen atom or a methyl group, R ₈ represents an alkyl group having 1 to 3 carbon atoms, and B represents -CH ₂ O (an alkyl group having 1 to 3 carbon atoms). A compound according to scope 1. 3 R ₁ represents a methyl group, R ₂ represents NO ₂ or NH ₂ , R ₃ represents a hydrogen atom, a methyl group, a chlorine atom or a bromine atom, and R ₄ and R ₅ are independently 3. The compound according to claim 2, wherein each represents a hydrogen atom or a methyl group, and R ₈ represents a methyl group or an isopropyl group. 4 N-(1'-methoxycarbonylethyl)-N-
Methoxyacetyl-2-methyl-6-aminoaniline, N-(1'-methoxycarbonylethyl)-N-methoxyacetyl-2-methyl-6-nitroaniline, N-(1'-methoxycarbonylethyl)-N- Methoxyacetyl-2,6-dimethyl-3-nitroaniline, N-(1'-methoxycarbonylethyl)-N-ethoxyacetyl-2,6-dimethyl-3-nitroaniline, N-(1'-isopropyloxycarbonyl ethyl)-N-methoxyacetyl-2,6-dimethyl-3-nitroaniline, N-(1'-methoxycarbonylethyl)-N-methoxyacetyl-2,6-dimethyl-3-aminoaniline, N-(1 '-methoxycarbonylethyl)-N-methoxyacetyl-2,3-dimethyl-6-aminoaniline and N-(1'-methoxycarbonylethyl)-N-methoxyacetyl-2,3-dimethyl-6-nitroaniline A compound according to claim 1 selected from the group consisting of: 5th order formula: (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₈ represent the meanings given in the following formula.) A pre-N-alkylated arylamino derivative represented by the following formula: A carboxylic acid represented by B-COOH () (where B represents the meaning given by the following formula) or its acid halide, acid anhydride or ester from 0 to
The following formula consists of N-acylation in the temperature range of 180°C: {In the formula, R ₁ represents an alkyl group having 1 to 3 carbon atoms or a halogen atom, R ₂ represents -NO ₂ or -NH ₂ , and R ₃ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, represents a group or a halogen atom, R ₄ is a hydrogen atom or has 1 to 3 carbon atoms
R ₅ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (However, the two ortho positions of the aniline part of the molecule are always substituted.) R ₈ represents the number of carbon atoms. 1 to 3 alkyl groups, B represents the following formula: -CH ₂ Z [wherein, Z represents the following formula: -X-R ₁₃ (wherein, X represents an oxygen atom or a sulfur atom, and R ₁₃ is represents a group represented by ) represents an alkyl group having up to 4 carbon atoms; } A method for producing a compound represented by. Sixth formula: (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and B represent the meanings given in the following formula.) A pre-N-acylated arylamino derivative represented by butyllithium, hydrogen activated with sodium chloride or alkali carbonate, the compound is converted to the following formula: (In the formula, R ₈ represents the meaning given by the following formula, and Y is a benzenesulfonyloxy group, p-bromobenzenesulfonyloxy group, p-tosyloxy group, trifluoroacetyloxy group, mesyloxy group, fluorine atom, chlorine atom , representing a bromine atom or an iodine atom) at a temperature range of 0 to 180°C. {In the formula, R ₁ represents an alkyl group having 1 to 3 carbon atoms or a halogen atom, R ₂ represents -NO ₂ or -NH ₂ , and R ₃ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, represents a group or a halogen atom, R ₄ is a hydrogen atom or has 1 to 3 carbon atoms
R ₅ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (However, the two ortho positions of the aniline part of the molecule are always substituted.) R ₈ represents the number of carbon atoms. 1 to 3 alkyl groups, B represents the following formula: -CH ₂ Z [wherein, Z represents the following formula: -X-R ₁₃ (wherein, X represents an oxygen atom or a sulfur atom, and R ₁₃ is represents a group represented by ) represents an alkyl group having up to 4 carbon atoms; } A method for producing a compound represented by. 7 Formula: {In the formula, R ₁ represents an alkyl group having 1 to 3 carbon atoms or a halogen atom, R ₂ represents -NO ₂ or -NH ₂ , and R ₃ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, represents a group or a halogen atom, R ₄ is a hydrogen atom or has 1 to 3 carbon atoms
R ₅ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (However, the two ortho positions of the aniline part of the molecule are always substituted.) R ₈ represents the number of carbon atoms. 1 to 3 alkyl groups, B represents the following formula: -CH ₂ Z [wherein, Z represents the following formula: -X-R ₁₃ (wherein, X represents an oxygen atom or a sulfur atom, and R ₁₃ is represents a group represented by ) represents an alkyl group having up to 4 carbon atoms; } A composition for controlling and/or preventing attack by harmful microorganisms, which contains at least one compound represented by the following. 8. The composition according to claim 7, which contains 0.01 to 90% by weight of the compound represented by the formula, 10 to 99.99% by weight of an auxiliary agent, and 0 to 33% by weight of a surfactant. 9. The composition according to claim 7 or 8, which contains a compound represented by the formula according to any one of claims 2 to 4. 10 Claim 1 obtained by homogeneously mixing a compound represented by the formula according to any one of claims 1 to 4 with a suitable carrier and/or surfactant. Composition according to item 7. 11. The composition according to claim 7, which is applied to plants or their cultivation areas in a microbicidally effective amount of the compound represented by the formula. 12. The composition according to claim 7, wherein the harmful microorganism is a plant pathogenic bacterium. 13 Claims 7 or 4, in which the compound represented by the formula according to any one of claims 1 to 4 is applied to plants or their cultivation areas in a finely dispersed form. Composition according to item 11.