RU2037493C1 - Amide derivatives - Google Patents

Abstract

FIELD: agriculture. SUBSTANCE: 2- (2,4-dimethylthiazol-5-carboxamido)-2-(2- furyl)acetonitrile, mp 108-109, the yield 74% 2-(2,4- dimethylthiazole-5-carboxamido)-2-(3-furyl)acitonitrile mp 94-96 C, the yield 74% 2-(2,4-dimethylthiazole-5- carboxamido)-2-(2-thienyl)acetonitrile, mp 127.5-128.5 C, the yield 65% EFFECT: improved properties of amide derivatives. 2 cl, 11 tbl

Description

 The invention relates to new derivatives of emide, their preparation and agricultural fungicides containing them.

 As the predominant agricultural fungicides for controlling plant diseases caused by mold, such as Pythiaccae and Peronosporaceae, keptan, captafol, dithiocarbamates and the like are known. However, they all have a preventive effect and are unlikely to have a therapeutic effect. Such fungicidal activity is insufficient to control plant diseases at the stage after the maturation of phytopathogenic fungi. This is a drawback, because depending on the circumstances, the use of fungicides is sometimes required after the initial development of phytopathogenic fungi. Therefore, there is always a significant need for a fungicide that exhibits not only high prophylactic activity, but also high systematic activity, such as a healing effect. This is especially important for the control of plant diseases, with rapidly appearing symptoms, such as those caused by Peronosporales. Recently, metalaxyl, that is, N- (2,6-dimethylphenyl) -N- (methoxyacetyl) elanine methyl ester, has excellent systematic activity and shows good healing effect. However, since the resistance of organisms to metalaxyl decreased shortly after its commercialization, its healing effect could not be highly appreciated. Under these circumstances, there is a need in the world for new fungicides with excellent systematic activity and showing a constant healing effect, especially fungicide, effectively applied to mildew of grapes.

(I) где R¹ и R² являются одинаковыми или различными и каждый обозначает атом водорода или С_1-3-алкильную группу и R³ обозначает 2-фурильную группу, 3-фурильную группу, 2-тиенильную группу или 3-тиенильную группу, проявляют сильную фунгицидную активность с отличной систематической активностью и целебным действием без фитотоксичности.As a result of intensive research, it was found that the amide compounds of formula I
R

(I) where R ¹ and R ² are the same or different and each represents a hydrogen atom or a C _1-3 alkyl group and R ³ represents a 2-furyl group, 3-furyl group, 2-thienyl group or 3-thienyl group, exhibit strong fungicidal activity with excellent systematic activity and healing effect without phytotoxicity.

(I-1) где R

обозначает метильную группу или этильную группу и R

обозначает 2-тиенильную группу или 3-тиенильную группу.Among the compounds of amide (I), preferred are compounds of formula I-1

(I-1) where R

denotes a methyl group or ethyl group and R

denotes a 2-thienyl group or a 3-thienyl group.

(I-2) где R

принимает указанные значения.Particularly preferred are compounds of formula I-2
H ₃ C

(I-2) where R

accepts the specified values.

 To date, a large number of amide compounds have been known that are beneficial fungicides and / or herbicides. Among them, amide (I) compounds are similar in chemical structure to the compounds of formula (I), where the thiazole ring is substituted with a substituted benzene, furan, thiophene, benzofuran or pyridine ring, the compounds of formula (I), where the thiazole ring is substituted with a substituted benzene ring, furan or a thiophene ring, a compound of formula (I) wherein the thiazole ring is substituted with a 4-substituted benzene ring, a compound of formula (I) where the thiazole ring is substituted with an alkyl, alkenyl, alkoxyalkyl, cycloalkyl, haloalkyl or ha loalkenyl group. However, the known compounds are not effective enough for plant diseases, especially diseases caused by phytopathogenic fungi, such as Peronosparales (e.g. mildew, late mold), as well as systematic activity. In addition, their phytotoxicity is significantly pronounced. Thus, the significant prophylactic and curative effect of amide (I) compounds, especially compound (I-2), on plant diseases caused by phytopathogenic fungi without manifesting any phytotoxicity is completely unexpected and does not follow from the known patents and publications.

(II) где R¹ и R² каждый принимают указанные значения, а аминонитрила формулы III
H₂N-

-R³ (III) где R³ принимает указанные значения, в их реакционно-способной форме. Некоторые типичные методики для осуществления указанного процесса будут далее объяснены в деталях.Compounds of amide (I) can be obtained, for example, by binding of a halide, carboxylic anhydride of the formula II

(II) where R ¹ and R ² each take the indicated meanings, and aminonitrile of the formula III
H ₂ N-

-R ³ (III) where R ³ takes the indicated values, in their reactive form. Some typical techniques for implementing this process will be further explained in detail.

 Method A.

(IV) где R¹ и R² каждый принимают определенные значения и Х обозначает атом галогена (например, хлор, бром), с аминонитрилом формулы (III) или его солью с получением соединения (I).According to this technique, a halide and an acid hydride of the formula (IV) are reacted.
R

(IV) where R ¹ and R ² each have certain meanings and X is a halogen atom (e.g. chlorine, bromine), with an aminonitrile of formula (III) or a salt thereof to give compound (I).

The reaction is generally carried out at a temperature of from -30 ^to 50 ° C, preferably from 0 ° ^C to room temperature for from 30 minutes to 24 hours, preferably 1-8 hours, typically in the presence of a base. Examples of the base are tertiary amines (e.g., pyridine, 4-dimethylaminopyridine, triethylamine, N, N-dimethylaniline, tributylamine, N-methylmorpholine), inorganic bases (e.g. sodium hydroxide, potassium hydroxide, calcium carbonate, sodium hydride) and so on. Aminonitrile (III) or its salt and base can be used, respectively, in amounts from 1 to 2 equiv. and from 1 to 3 equiv. to 1 eq. acid halide and hydride (IV). In addition, aminonitrile (III) itself can also be used as a base. Optionally, any solvent may be used in the reaction, and examples thereof include: aliphatic hydrocarbons (e.g., hexane, heptane, naphtha, petroleum ether), aromatic hydrocarbons (e.g., benzene, toluene, xylene), halogenated hydrocarbons (e.g., chloroform, carbon tetrachloride , dichloroethane, chlorobenzene, dichlorobenzene), ethers (e.g. diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohec anon), esters (e.g. ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate), nitro compounds (e.g. nitromethane, nitrobenzene), nitriles (e.g. acetonitrile, isobutyl nitrile), acid amides (e.g., formamide, N, N-dimethylformamide, N, N-dimethylacetamide), sulfur compounds (e.g. dimethyl sulfoxide, sulfolane) and so on. Water is also suitable as a solvent, although it cannot be used for any water-based base, such as sodium hydride. These solvents may be used alone or in combination.

 After completion of the reaction, the reaction mixture can be post-processed by itself in a standard manner, for example, by washing it with water, separating and concentrating the organic layer and, optionally, purifying the resulting product. Chromatography or recrystallization may be used for purification.

 Method B.

(V) и получение ацилимидазола формулы (VI)
R

(VI) где R¹ и R² каждый принимают определенные значения, и затем проводят реакцию ацилимидазола (VI) с аминонитрилом (III) или его солью с получением соединения амида (I).According to this technique, a carboxylic acid (II) is reacted with N, N ¹ -thionyl diimidazole of the formula (V)

(V) and obtaining acylimidazole of the formula (VI)
R

(VI) where R ¹ and R ² each take on certain meanings, and then the acylimidazole (VI) is reacted with aminonitrile (III) or a salt thereof to obtain an amide compound (I).

Reactions in the initial and subsequent stages are usually carried out sequentially without isolation of acylimidazole (VI), since it is not stable enough. These reactions may be carried out at a temperature of from -30 ^to 50 ° C, preferably from 0 ° ^C to room temperature for from 30 minutes to 24 hours, preferably from 1 to 8 hours. The ratio of carboxylic acid (II), N, N ^1- thionyl diimidazoles (V) and aminonitrile (III) or its salt is usually 1 1 1-2 eq. Optionally, any solvent may be used in the reaction, examples of these solvents are those given as examples in Method A, but the use of water should be avoided.

 After completion of the reaction, the reaction mixture can be post-treated by itself in a standard manner, for example, washing it with water, separating and concentrating the organic layer and, optionally, purifying the resulting product. Chromatography or recrystallization may be used for purification.

In these methods, some of the carboxylic acids (II) and acid halides (IV) are known, others can be obtained by known methods, for example, 2,4-disubstituted thiazole-5-carboxylic acids, 2,4-disubstituted thiazole-5-carbonyl chloride , N, N ¹ -thionyldiimidazole.

 Aminonitrile (III) is easily obtained by the reaction of the corresponding aldehyde with ammonia and potassium or sodium cyanide according to the Strecker reaction.

 The amide compounds (I) of the invention have one asymmetric carbon atom in their molecules, so that there are two optical isomers for them. Practical embodiments of the preparation of the amide (I) compound are shown in the examples.

PRI me R 1 (connection 1). To a solution of imidazole (2.72 g, 40 mmol) in dry tetrahydrofuran (60 ml) was added dropwise thionyl chloride (1.20 g, 10 mmol) under ice cooling with stirring. After that, the temperature of the resulting mixture was brought to room temperature and 2,4-dimethyl-5-thiazolecarboxylic acid (1.57 g 10 mol) was added to the mixture at one time and stirring was continued for 30 minutes, resulting in 5-imidazolylcarbonyl-2 , 4-dimethylthiazole. To the mixture was added dropwise a solution of 2- (2-furyl) aminoacetonitrile (1.46 g, 12 mmol) in dry tetrahydrofuran under ice cooling, and the resulting mixture was stirred at room temperature for 1 h. After completion of the reaction, tetrahydrofuran was removed under reduced pressure until separation of the residue. Water was added to the residue and extracted with ethyl acetate. The ethyl acetate layer was washed twice with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain crude crystals. Recrystallization from ethanol yields 2.0 g of 2- (2,4-dimethylthiazol-5-carboxamido) -2- (2-Fu-reel) acetonitrile as colorless crystals of melting point 108-109 ^C. Yield: 74%
PRI me R 2 (connection 2). To a solution of 2- (3-furyl) aminoacetonitrile (1.46 g, 12 mmol) and triethylamine (1.20 g, 12 mmol) in tetrahydrofuran (30 ml), a solution of 2,4-dimethylthiazole-5-carbonyl chloride (1 , 75 g, 10 mmol) in tetrahydrofuran (10 ml) under ice cooling. After addition, the temperature of the mixture was brought to room temperature and stirring was continued for 3 hours. The solvent was removed under reduced pressure to separate the residue. Water was added to the residue and extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a crude oil. The oil is purified by silica gel column chromatography (eluent: n-hexane-ethyl acetate 2 1 by volume) to obtain 1.93 g of 2- (2,4-dimethylthiazole-5-carboxamido) -2- (3-furyl) acetonitrile as colorless crystals with a melting point of 94-96 ^about C. Yield 74%
PRI me R 3 (connection 3). Thionyl chloride (1.20 g, 10 mmol) was added dropwise to a solution of imidazole (2.27 g, 40 mmol) in dry tetrahydrofuran (60 ml) under ice cooling with stirring. After the temperature of the resulting mixture was brought to room temperature, 2,4-dimethyl-5-thiazolecarboxylic acid (1.57 g, 10 mmol) was added to the mixture at one time, and stirring was continued for 30 minutes. To the mixture was added dropwise a solution of 2- (2-thienyl) aminoacetonitrile (1.65 g, 12 mmol) in dry tetrahydrofuran under ice cooling, and the resulting mixture was stirred at room temperature for 1 hour. After completion of the reactions, tetrahydrofuran was removed under reduced temperature. pressure until separation of the residue. Water was added to the residue and extracted with ethyl acetate. The ethyl acetate layer was washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a crude oil. The oil is purified by silica gel column chromatography (eluent n-hexane-ethyl acetate 2 1 by volume) to obtain crude crystals. Recrystallization from n-hexene-ethyl acetate gave 1.80 g of 2- (2,4-dimethylthiazole-5-carboxamido (2- (2-thienyl) acetonitrile as colorless crystals with a melting point of 127.5-128.5 ^about C. Yield 65%
PRI me R 4 (connection 4). To a solution of imidazole (2.72 g, 40 mmol) in dry tetrahydrofuran (60 ml) was added dropwise thionyl chloride (1.20 g, 10 mmol) under ice cooling with stirring. After the temperature of the resulting mixture was brought to room temperature, 2,4-dimethyl-5-thiazolecarboxylic acid was added to the mixture at a time, and stirring was continued for another 30 minutes. To the mixture was added dropwise a solution of 2- (3-thienyl) aminoacetonitrile (1.65 g, 12 mmol) in dry tetrahydrofuran under ice cooling, and the resulting mixture was stirred at room temperature for 1 hour. After completion of the reaction, tetrahydrofuran was removed under reduced temperature. pressure until separation of the residue. Water was added to the residue and extracted with ethyl acetate. The ethyl acetate layer was washed twice with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a crude oil. The oil was purified by silica gel column chromatography (eluent n-hexane-ethyl acetate 2 1 v / v) to obtain crude crystals. Recrystallization from n-hexane-ethyl acetate yields 1.95 g of 2 (2,4-dimethylthiazole-5-carboxamido) -2- (3-thionyl) acetonitrile as colorless crystals melting at 94-95 ° ^C. Yield 70%
PRI me R 5 (connection 5). To a solution of imidazole (2.72 g, 40 mmol) in dry tetrahydrofuran (60 ml) was added dropwise thionyl chloride (1.20 g, 10 mmol) under ice cooling with stirring. After the temperature of the resulting mixture was brought to room temperature, 2-methyl-4-ethyl-5-thiazolecarboxylic acid (1.71 g, 10 mmol) was added to the mixture at a time, and stirring was continued for another 30 minutes. To the mixture was added dropwise a solution of 2- (2-furyl) aminoacetonitrile (1.46 g, 12 mmol) in dry tetrahydrofuran under ice cooling, and the resulting mixture was stirred at room temperature for 1 hour. After completion of the reaction, tetrahydrofuran was removed under reduced pressure. before separation of the precipitate. Water was added to the residue and extracted with ethyl acetate. The ethyl acetate layer was washed twice with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a crude oil. The oil is purified by column chromatography (eluent n-hexane-ethyl acetate 2 1 by volume) to obtain crude crystals. Recrystallization from n-hexane-ethyl acetate yields 1.59 g of 2- (2-methyl-n-ethylthiazole-5-carboxamido) -2- (2-furyl) acetonitrile as colorless crystals with a melting point ^of 125-126 C. Yield 57%
PRI me R 6 (connection 6). To a solution of imidazole (2.72 g, 40 mmol) in dry tetrahydrofuran (60 ml) was added dropwise thionyl chloride (1.20 g, 10 mmol) under ice cooling with stirring. After the temperature of the resulting mixture was brought to room temperature, 2-methyl-4-ethyl-5-thiazolecarboxylic acid (1.65 g, 10 mmol) was added to the mixture at a time, and stirring was continued for 30 minutes. To the mixture was added dropwise a solution of 2- (2-thienyl) aminoacetonitrile (1.65 g, 12 mmol) in dry tetrahydrofuran under ice cooling, and the resulting mixture was stirred at room temperature for 1 hour. After completion of the reaction, tetrahydrofuran was removed under reduced temperature. pressure until separation of the residue. Water was added to the residue and extracted with ethyl acetate. The ethyl acetate layer was washed with water twice, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a crude oil. The oil is purified by silica gel column chromatography (eluent, n-hexane ethyl acetate 2 1 by volume) to obtain crude crystals. Recrystallization from n-hexane ethyl acetate affords 2- (2-methyl-4-ethylthiazole-5-carboxamido) -2- (2-thienyl) acetonitrile as colorless crystals of melting point 137-138 ^C. Yield: 60%
PRI me R 7 (connection 7). Thionyl chloride (1.20 g, 10 mmol) was added dropwise to a solution of imidazole (2.72 g, 40 mmol) in dry tetrahydrofuran (60 ml) under ice cooling with stirring. After the resulting mixture was brought to room temperature, 2-methyl-4-n-propyl-5-thiocarboxylic acid (1.85 g, 10 mmol) was added to the mixture at a time, and stirring was continued for another 1 hour. K the mixture was added dropwise a solution of 2- (2-thienyl) aminoacetonitrile (1.65 g, 12 mmol) in dry tetrahydrofuran under ice cooling, and the resulting mixture was stirred at room temperature for 3 hours. After completion of the reaction, tetrahydrofuran was removed under reduced pressure before separation of the residue. The ethyl acetate layer was washed twice with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a crude oil. The oil is purified by silica gel column chromatography (eluent n-hexane-ethyl acetate 2 1 v / v) to obtain crude crystals. Recrystallization from n-hexane-ethyl acetate gives 1.61 g of 2- (2-methyl-4-n-propylthiazole-5-carboxyamido) -2- (2-thienyl) acetonitrile as colorless crystals with a melting point of 125-126 ^about C. Yield 53%
PRI me R 8 (connection 9). Thionyl chloride (1.20 g, 10 mmol) was added dropwise to a solution of imidazole (2.72 g, 40 mmol) in dry tetrahydrofuran (60 ml) under ice cooling with stirring. After the temperature of the resulting mixture was brought to room temperature, 2-methyl-4-isopropyl-5-thiazolecarboxylic acid (1.85 g, 10 mmol) was added at a time to the mixture, and stirring was continued for 1 hour. Dropwise to the mixture. a solution of 2- (2-thienyl) aminoacetonitrile (1.65 g, 12 mmol) in dry tetrahydrofuran was added under ice cooling, and the resulting mixture was stirred at room temperature for 3 hours. After completion of the reaction, tetrahydrofuran was removed under reduced pressure to separate the residue . Water was added to the residue and extracted with ethyl acetate. The ethyl acetate layer was washed twice with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a crude oil. The oil was purified by silica gel column chromatography (eluent n-hexane ethyl acetate 2 1 by volume) to obtain 1.49 g of 2- (2-methyl-4-isopropylthiazole-5-carboxyamido (2- (2-thienyl) acetonitrile as a viscous oil. NMR δ (CDCl ₃ ) 1.26 / 6H, doublet, J 6 Hz), 2.62 / 3H, singlet), 3.70 / 1H, septet J 6 Hz), 6.35 / 1H, doublet, J = 8 Hz), 6.8 - 7.1 (4H, multiplet). Yield 49%
According to the specified method, amide (I) compounds are obtained, are presented in table. 1.

 For the practical use of the compounds of amide (I) as fungicides, they can be used on their own or in compositions, such as emulsion concentrates, wettable powders, suspensions, powders or granules. Such compositional forms can be formed essentially by standard methods, for example, by mixing at least one of the amide compounds (I) with the appropriate solid or liquid carrier (s) or diluent (s) and, if necessary, with the corresponding additive (s) (e.g. surfactants, binders, dispersants, stabilizers) to improve the dispersibility and other properties of the active ingredient.

 Examples of solid carriers or diluents are powders or granules of kaolin, attapulgite, bentonite, acid mica, pyrophyllite, talc, diatomaceous earth, calcite, corn stalk powder, nut powder, urea, ammonium sulfate, synthetic hydrated silicon oxide, and so on. Aromatic hydrocarbons (e.g., xylene, methylnaphthalene), alcohols (e.g., isopropanol, cellulose ethylene glycol), ketone (e.g., acetone, cyclohexanone, isophorone), soybean oil, cottonseed oil, dimethyl sulfoxide, acetonitrile, can be presented as a liquid carrier or diluent. water and so on.

 The surface active agent used for emulsification, dispersion or spraying may be any anionic or nonionic agent. Examples of the surfactant include anionic surfactants and nonionic surfactants such as alkyl sulfates, alkylaryl sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl phosphates, naphthalene sulfonic acid and formalin condensates, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene polymers, polyoxyethylene copolymers. sorbitan and fatty acids; and polyoxyethylene sorbitan fatty acid esters. Examples of auxiliary agents include ligninsulfonates, sodium alginate, polyvinyl alcohol, gum arabic, SMS (carboxymethyl cellulose), PAP (isopropyl acid phosphate) and so on.

 In order to obtain a fungicidal effect, the amide (I) compounds can be used at doses from 0.01 to 50 g, preferably from 0.05 to 10 g per ar (0.01 ha). Typically, the concentration of the active ingredient in the fungicidal composition of the invention may vary from 0.01 to 99.9 wt. preferably from 1 to 90 wt. For practical use, the composition obtained in this form is usually diluted with water to a concentration of from 0.0001 to 0.5 wt. preferably from 0.0005 to 0.2 wt. active ingredient and then used after such dilution. However, when the composition is formed in the form of dusts or granules, it is usually used without any dilution.

 It should also be noted that the compounds of amide (I) can be used in a mixture with other fungicides to enhance their fungicidal activity. In addition, they can be used with insecticides, miticides, nematicides, herbicides, plant growth regulators, fertilizers and so on.

 As indicated, the compounds of amide (I) show reading fungicidal activity. For example, they exhibit a preventive, healing and systematic effect against a wide range of plant diseases caused by phytopathogenic fungi, typical examples of which are mildew of vegetables or radishes (Peronospora brassicae), spinach (Peronospora spinaciae), tobacco (Peronospora tabacina), and cucumber (Pseudoperonosra) , grapes (Plasmopara viticola) or parsley (Plasmopara nivea), rot of apple, strawberry or panax (Phytophthora cactorum), tomato or cucumber (Phytophthora copsici), pineapple (Phytophthora cinnamomi), potato, tomato or eggplant (Phytoptophthans) forage bean or onion (Phytophthora nico tranae var. nicotianae), black leg of spinach (Phythium sp.) or cucumber (Phythium aphanidermatum), rot of the root of wheat (Phytium sp.) black leg of sprouts of tobacco (Pythium debaryanum), Phythium rot of soybeans (Phythium aphanidermatanum, P.) P./irregulari, P. myiotylum, P. ultimam and so on.

 Some practical embodiments of the fungicidal composition according to the invention are illustratively shown in the following composition examples.

 An example of the composition 1. 50 wt. h of each of the compounds 1-14, 3 wt.h. calcium ligninsulfonate, 2 parts by weight sodium auryl sulfonate and 45 parts by weight synthetic hydrated silica is mixed and carefully ground to obtain a wettable powder.

 An example of the composition 2. 25 wt.h. each of compounds 1-14, 3 parts by weight polyoxyethylene sorbate monooleate, 3 parts by weight SMS and 69 wt. water was mixed and thoroughly ground to obtain particles less than 4 microns in size to obtain a suspension.

 An example of the composition 3. 2 wt.h. each of compound 1-14, 88 parts by weight kaolin and 10 parts by weight talcum powder was mixed and ground finely to obtain a powder.

 An example of the composition 4. 20 wt.h. each of compounds 1-14, 14 parts by weight polyoxyethyleneostyrylphenyl ether, 6 parts by weight calcium dodecylbenzenesulfonate and 60 wt. including xylene was mixed together to obtain an emulsion concentrate.

 An example composition 5. 2 wt.h. each of compounds 1-14, 1 parts by weight synthetic hydrated silica, 2 parts by weight calcium ligninsulfonate, 30 parts by weight bentonite and 65 parts by weight kaolin was mixed and thoroughly sprayed with added water to obtain granules.

 Typical test data showing significant fungicidal activity of amide (I) compounds are presented below. Estimates are presented as percent of disease control: 100% means no infection; 0% means that the plant is completely infected compared to the control plant.

 For comparison, we used the compounds shown in table. 2.

 Test Example 1. Prophylactic effect on potato rot (Phytophthora infestans).

 A plastic pot is filled with sandy soil and potatoes (Danshaku) are planted in it, after which cultivation is carried out in a greenhouse for 40 days. A test compound formed in the form of a wettable powder according to Example Composition 1 and diluted with water to a certain concentration is carefully sprayed on the sprouts of the test plants, and the test plants are inoculated with a spray of Phytophthora infestans spore suspension, after which the plants are kept overnight in humid conditions. Then the plants sprout for 5 days under lighting and observation. The results are presented in table. 3.

 Test Example 2

Healing effect on potato rot (Phytophthora infestans). A plastic pot is filled with sandy soil and potatoes (Danshaku) are planted in it, after which cultivation is carried out in a greenhouse for 40 days. Spore suspension of Phytophthora infestans was inoculated by spraying the test plants over the sprouts, which are then allowed to stand overnight at 20 ° ^C in humid conditions. The test compound, formed as a wettable powder according to example composition 1 and diluted with water to a certain concentration, is carefully sprayed over the test plants, which then further grow for 5 days under lighting and observation. The results are presented in table. 3.

 Test Example 3. Prophylactic against rot of tomato (Phytophthora infestans).

A plastic pot is filled with sandy soil and tomato seeds (Ponte Rosa) are sown in it, after which cultivation is carried out in a greenhouse for 20 days. The test compound, formed in the form of a wettable powder according to example composition 1 and diluted with water to a certain concentration, is carefully sprayed over the sprouts at the stage of 2-3 leaves of the test plants and the Phytophthora infestans spore suspension is inoculated by spraying over the test plants, after which the plants are left in high humidity at ²⁰ ° C overnight. Further, the test plants grow for 5 days under lighting and under observation. The results are presented in table. 3.

 Test Example 4. Medicinal effect against rot of Phytophthora infestans tomato.

A plastic pot is filled with sandy soil and tomato seeds (Ponte Rosa) are sown in it, after which cultivation is carried out in a greenhouse for 20 days. Phytophthora infestans spore suspension was inoculated by spraying on the sprouts at the 2-3 leaf stage of the test plants, then the plants are left in high humidity conditions at ²⁰ ° C overnight. Test compounds formed in the form of a wettable powder according to example composition 1 and diluted with water to a certain concentration are carefully sprayed over the test plants, after which they are allowed to grow for 5 days under illumination and under observation. The results are presented in table. 3.

 Test Example 5. Prophylactic action against mildew of Plasmopara viticola grapes.

A plastic pot is filled with sandy soil and grape seeds (Berry-A) are sown in it, and then cultivated in a greenhouse for 50 days. The test compound, formed in the form of a wettable powder according to example composition 1 and diluted with water to a certain concentration, is thoroughly sprayed over the sprouts at the stage of 6-7 leaves of the test plants, and the Plasmopara viticola spore suspension is inoculated by spraying over the test plants, after which they are left under conditions humidity at ²⁰ ° C overnight. Further, the test plants are allowed to grow for 8 days under lighting and under observation. The results are presented in table. 3.

 Test Example 6. Medicinal effect against mildew of Plasmopara viticola grapes.

A plastic pot is filled with sandy soil and grape seeds (Barry-A) are sown in it, after which cultivation is carried out in a greenhouse for 50 days. Plasmopara viticola spore suspension was inoculated by spraying on the sprouts in step 6-7 leaf of the test plants, and then leaving them in a humid environment at ²⁰ ° C overnight. The test compound, formed in the form of a wettable powder according to example composition 1 and diluted with water to a certain concentration, is carefully sprayed over the test plants, after which they are allowed to grow for 8 days under lighting and under observation. The results are presented in table. 3.

 Test Example 7. Prophylactic action against mildew of cucumber Pseudoperonospora cubensis.

The plastic pot is filled with sandy soil and the seeds of cucumber (Sagamihanjiro) are sown in it, after which cultivation is carried out in the greenhouse for 14 days. The test compound is formed in the form of a wettable powder according to Formulation Example 1 and diluted with water to a predetermined concentration, thoroughly sprayed over the sprouts of the test plants, and a spore suspension of Pseudoperonospora cubensis was inoculated by spraying on the test compounds are then left overnight at ²⁰ ° C and in wet conditions. Further, the test plants grow for 5 days under lighting and under observation. The results are presented in table. 3.

 Test Example 8. Medicinal effect against mildew of cucumber Pseudoperonospora cubensis.

The plastic pot is filled with sandy soil and the seeds of the cucumber (Sagamihanjiro) are sown, after which cultivation is carried out in the greenhouse for 14 days. The spore suspension Pseudoperonospora cubensis was inoculated by spraying on the test plants shoots are then left overnight at ²⁰ ° C and in wet conditions. The test compound, formed in the form of a wettable powder according to example composition 1 and diluted with water to a certain concentration, is carefully sprayed over the test plants, which then grow for 8 days under lighting and under observation. The results are presented in table. 3.

 Test Example 9. Soil test against rot of Phytophthora infestans tomato.

Plastic pots are filled with sandy soil and sown tomato seeds (Ponte Rosa) in them, and then cultivated in a greenhouse for 20 days. When the sprouts have reached the 2-3 leaf stage, the test compounds formed in the form of an emulsion concentrate according to Example 4 and diluted with water to a certain concentration are poured into the soil and the test plants remain in the greenhouse overnight. Phytophthora infestans spore suspension was inoculated by spraying over the test plants, which were then left at ²⁰ ° C overnight in high humidity conditions. Further, the test plants grow for 5 days under lighting and under the supervision of a preventive effect. The results are presented in table. 4.

 Test Example 10

 Phytotoxicity.

 Above the sprouts of grapes (Berry-A), tomato (Ponte Rosa) and cucumber (Sagamihanjiro), the test compound is formed in the form of a wettable powder according to example composition 1 and diluted with water to a certain concentration, and allow the test plants to grow in a greenhouse for 2 weeks under the supervision of phytotoxicity for test plants. Phytotoxicity is evaluated visually on a scale of 0, 1, 2, 3, 4, or 5 depending on the degree of damage, where 5 indicates the absence of plant growth due to phytotoxicity, and 0 indicates the absence of phytotoxicity. The results are presented in table. 5.

 Test example 11. Preventive action against the boiling of cucumbers from (Phythium aphanidermatum).

The test compound in the form of granules prepared according to the formulation of Example 5 is applied to sandy soil infected with Phythium aphanidermatum. The soil prepared in this way is filled with a plastic pan planted with cucumber seeds (Sagamihanjiro variety). The experimental plants were cultured for 11 days at 27 ^{° C} under illumination and observed in relation to preventive action. The results are shown in table. 6.

 Test example 12. Preventive action against damage to potato plants, characterized by wilting them and falling leaves without rotting (caused by Phytophthora infestans fungi).

A plastic baking sheet is filled with sandy soil and planted with potatoes (Danashaku cultivar), followed by cultivation in a greenhouse for 40 days. The test compound is used as part of an emulsifiable concentrate according to the formulation of Example 4 and diluted with water to the desired concentration. The resulting solution was thoroughly sprayed seedlings on their outer surfaces of the test plants and then inoculated with a spore suspension of Phytophthora infestans by spreading over the test plants, which was allowed to stand at ²⁰ ° C overnight in a humidity condition. Next, the test plants are additionally grown for 5 days under lighting and observation. The results are shown in table. 7.

 Test example 13. The healing effect against damage to potato plants, characterized by wilting them and falling leaves without rotting (caused by Phytophthora infestans fungi).

A plastic baking sheet is filled with sandy soil and planted with potatoes (Danashaku cultivar), after which they are cultivated in a greenhouse for 40 days. The spores suspension of Phytophthora infestans was inoculated by spreading over the seedlings of the test plants, which thereupon allowed to stand at ²⁰ ° C overnight in a humidity condition. The test compound in the formulation of an emulsifiable concentrate according to the formulation of Example 4 is diluted with water to the prescribed concentration. The test solution is thoroughly sprayed with the obtained solution on the surface of the test plants and additionally grown for 5 days under lighting and observation. The results are shown in table. 7.

 Test example 14. Preventive action against late damage to tomato plants, characterized by withering and falling leaves without rotting (caused by Phytophthora infestans fungi).

A plastic baking sheet is filled with sandy soil and planted with tomato seedlings (Ponte Rosa variety), then cultivated in a greenhouse for 20 days. The test compound is introduced into the composition of an emulsifiable concentrate according to the formulation of example 4 and diluted with water to the prescribed concentration. The resulting solution is thoroughly sprayed with the surface of the seedlings at the stage of 2-3 leaves, and the test plants were inoculated with a spore suspension of Phytophthora infestans by the distribution of the test plants, which are allowed to stand at 20 ° ^C overnight in a humid environment. Further, the experimental plants are additionally grown for 5 days under lighting and observation. The results are shown in table. 7.

 Test example 15. The healing effect against late damage to tomato plants, characterized by withering and falling leaves without rotting (caused by Phytophthora infestans fungi).

A plastic baking sheet is filled with sandy soil and planted with tomato seedlings (Ponte Rosa variety), followed by cultivation in a greenhouse for 20 days. Inoculate a suspension of Phytophthora infestans spores by distributing seedlings of experimental plants that are at the developmental stage of 2-3 leaves. The plants were then allowed to stand at 20 ° ^C overnight in a humid environment. The test compound is incorporated into an emulsifiable concentrate according to the formulation of Example 4 and diluted with water to a prescribed concentration. The solution is carefully sprayed over the test plants. They are additionally grown for 5 days under lighting and observation. The results are shown in table. 7.

 Test Example 16. Preventive action against downy mildew (mildew) of grape plants caused by Plasmopara viticola.

The plastic pan is filled with sandy soil and planted with grape plants (Barry-A variety), which are then cultivated in the greenhouse for 50 days. The test compound in the composition of an emulsifiable concentrate according to the recipe of example 4 is diluted with water to the prescribed concentration. The solution carefully sprayed outside seedlings at the stage of development of 6-7 leaves. The test plants are inoculated with a Plasmopara viticola spore suspension by distribution over the test plants. They were allowed to stand at 20 ° ^C overnight in a humid environment. The test plants are grown for 8 days under lighting and observed. The results are shown in table. 7.

 Test Example 17. Healing effect against downy mildew (mildew) of grape plants caused by Plasmopara viticola.

A plastic pan is filled with sandy soil and planted with grape plants (Barry-A variety), followed by cultivation in a greenhouse for 50 days. The Plasmopara viticola spore suspension is inoculated by distribution of 6 to 7 leaves in the test plants over seedlings at the developmental stage. Then they are left to stand at 20 ° ^C overnight in a humid environment. The test compound in the composition of an emulsifiable concentrate according to the recipe of example 4 is diluted with water to the prescribed concentration. The resulting solution is carefully sprayed onto the surface of the test plants, which are additionally grown for 8 days under lighting and observation. The results are shown in table. 7.

 Test Example 18. Preventive action against downy mildew (mildew) of cucumbers caused by Pseudoperonospora cubensis.

A plastic pan is filled with sandy soil and planted with cucumber seeds (Sagamihanjiro variety), then cultivated in a greenhouse for 14 days. The test compound in the composition of an emulsifiable concentrate according to the formulation of Example 4 is diluted with water to the prescribed concentration and the seedlings of the test plants are thoroughly sprayed with the resulting solution from the outside. Spore suspension of Pseudoperonospora cubensis was inoculated by spreading on the test plants, which are allowed to stand at 20 ° ^C overnight in a humid environment. The test plants are additionally grown for 5 days under lighting and observation. The results are shown in table. 7.

 Test Example 19. Healing effect against downy mildew (mildew) of cucumbers caused by Pseudoperonospora cubensis.

The plastic pan is filled with sandy soil and sown with cucumber seeds (cultivar: Sagamihanjiro), followed by cultivation in the greenhouse for 14 days. Spore suspension of Pseudoperonospora cubensis was inoculated by spreading on the test plants, which were then allowed to stand at 20 ° ^C overnight in a humid environment. An emulsifiable concentrate containing the test compound in the formulation of Example 4 and diluted with water to the prescribed concentration is used to thoroughly spray the seedlings of the test plants. They are additionally grown for 8 days under lighting and observation. The results are shown in table. 7.

 Test example 20. Preventive action against damage to potato plants, characterized by wilting them and falling leaves without rotting (caused by Phytophthora infestans fungi). A plastic baking sheet is filled with sandy soil and potatoes are planted there (Danshaku cultivar), followed by cultivation in a greenhouse for 40 days.

The test compound in the composition of the powders corresponding to the formulation of Example 3 is dissolved in water and diluted to the prescribed concentration and used for thorough spraying over the seedlings of the test plants. The spores suspension of Phytophthora infestans was inoculated distribution of the test plants, which were then allowed to stand at ²⁰ ° C overnight in a humid environment. These plants are additionally grown for 9 days under lighting and observation. The results are shown in table. 8.

 Test example 21. The healing effect against damage to potato plants, characterized by wilting them and falling leaves without rotting (caused by Phytophthora infestans fungi).

A plastic baking sheet is filled with sandy soil and potato tubers are planted (Danshaku variety). Then cultivated in a greenhouse for 40 days. Spore suspension of Phytophthora infestans was inoculated by distributing seedlings of the test plants, which are allowed to stand at 20 ° ^C overnight in a humid environment. The test compound in the composition of the powders corresponding to the formulation of Example 3 is diluted with water to the intended concentration and the resulting solution is thoroughly sprayed on top of the test plants, which are subsequently further grown for 5 days under illumination and observation. The results are shown in table. 8.

 Test Example 22. Preventive action against late damage to tomato plants, characterized by wilting and leaf decay without rotting caused by Phytophthora infestans.

A plastic baking sheet is filled with sandy soil and inoculated with tomato seedlings (Ponte Rosa variety), followed by cultivation in a greenhouse for 20 days. The test compound in the composition of the powders corresponding to the formulation of example 3 is dissolved in water and diluted to the prescribed concentration. The resulting solution thoroughly sprayed the surface of the seedlings at the stage of development of 2-3 leaves of the test plants. The spores of Phytophthora infestans was inoculated slurry distribution on the test plants, which was allowed to stand at ²⁰ ° C overnight in a humid environment. Test compounds are further grown for 5 days under illumination and observation. The results are shown in table. 8.

 Test example 23. The healing effect against late damage to tomato plants, characterized by wilting them and falling leaves without rotting (caused by Phytophthora infestans fungi).

A plastic baking sheet is filled with sandy soil and planted with tomato seedlings (Ponte Rosa variety), followed by cultivation in a greenhouse for 20 days. Phytophthora infestans spore suspension is inoculated by distribution of 2-3 leaves of test plants to seedlings at the developmental stage. The plants were then allowed to stand at 20 ° ^C overnight in a humid environment. The test compound in the composition of the powders, the formulation of which is indicated in example 3, is dissolved in water, diluted with water to the specified concentration and the test plants are thoroughly sprayed with the resulting solution, which are additionally grown for 5 days under illumination and observation. The results are shown in table. 8.

 Test Example 24. Preventive effect against downy mildew (mildew) of grape plants (Plasmopara viticola).

The plastic pan is filled with sandy soil and planted with vines (grade Berry-A) and cultivated in a greenhouse for 50 days. Powders containing the test compound according to the formulation of Example 3 are dissolved in water and diluted to the prescribed concentration. The resulting solution is thoroughly sprayed with the seedlings of the test plants at the developmental stage of 6-7 leaves. Spores of Plasmopara viticola in suspension are inoculated by distribution to experimental plants. They were allowed to stand at 20 ° ^C overnight in a humid environment. The test plants are additionally grown for 8 days under lighting and observation. The results are shown in table. 8.

 Test Example 25. Healing effect against downy mildew (mildew) in vines caused by Plasmopara viticola.

A plastic baking sheet is filled with sandy soil and seedlings of vines (cultivar Berry-A) are planted there, followed by cultivation in a greenhouse for 50 days. Plasmopara viticola spore suspension is inoculated by distributing from seedlings of test plants at the developmental stage from 6 to 7 leaves. Then, these plants are allowed to stand at 20 ° ^C overnight in a humid environment. The test compound in the composition of the powders corresponding to the formulation of example 3 is dissolved in water and diluted to the intended concentration. The test solution was thoroughly sprayed with the obtained solution from the outside of the test plants, and they were additionally grown for 8 days under lighting and observation. The results are shown in table. 8.

 Test Example 26. Preventing action on downy mildew (mildew) of cucumbers caused by Pseudoperonospora cubensis.

The plastic baking sheet is filled with sandy soil and cucumber seedlings are planted there (Sagamihanjiro variety), after which they are cultivated in the greenhouse for 14 days. The test compound in the composition of the powders according to the recipe of example 3 is dissolved in water and diluted to the intended concentration. The resulting solution is thoroughly sprayed outside the seedlings of the test plants. Spores of Pseudoperonospora cubensis, located in the suspension were inoculated by distributing them on the test plants, which was allowed to stand at ²⁰ ° C overnight in a humid environment. The test plants are additionally grown for 5 days under lighting and observation. The results are shown in table. 8.

 Test Example 27. Healing effect on downy mildew (cucumber mildew) caused by Pseudoperonospora cubensis.

A plastic baking sheet is filled with sandy soil and seedlings of cucumber (Sagamihanjiro variety) are planted there, after which they are cultivated in the greenhouse for 14 days. The spores suspension of Pseudoperonospora cubensis was inoculated in distribution outside the seedlings of the test plants, which were then allowed to stand overnight at ²⁰ ° C under humid conditions. The test compound in the composition of the powders according to the recipe of example 3 is dissolved in water, diluted to the intended concentration and the test plants are thoroughly sprayed with the resulting solution from the outside. They are additionally grown for 8 days under lighting and observation. The results are shown in table. 8.

 Test Example 28. Preventive effect against damage to potato plants characterized by withering and falling leaves without rotting (caused by Phytophthora infestans fungi).

The plastic pan is filled with sandy soil and potato tubers are planted there (cultivar: Danshaku) and cultivated in the greenhouse for 40 days. The test compound in the suspension according to the recipe of Example 2 is dissolved in water and the resulting solution, diluted to the prescribed concentration, carefully sprayed over the seedlings of the test plants. Then Phytophthora infestans spores in the composition of the suspension were inoculated with the distribution of the test plants, which are allowed to stand at 20 ° ^C overnight in a humid environment. The test plants are additionally grown for 5 days under lighting and observation. The results are shown in table. nine.

 Test example 29. Healing effect against damage to potato plants, characterized by withering and falling leaves without rotting (caused by Phytophthora infestans fungi).

A plastic baking sheet is filled with sandy soil and potato tubers are planted there (Danshaku cultivar) and cultivated in a greenhouse for 40 days. Phytophthora infestans spores in the suspension was inoculated on the test plants distribution, which was allowed to stand at ²⁰ ° C overnight in a humid environment. A suspension containing the test compound corresponding to the formulation of Example 2 is diluted with water to the intended concentration and the resulting solution is carefully sprayed over the test plants. They are additionally grown for 5 days under lighting and observation. The results are shown in table. nine.

 Test example 30. The preventive effect against damage to tomato plants, characterized by wilting them and falling leaves without rotting (caused by Phitophthora infestans fungi).

A plastic baking sheet is filled with sandy soil and planted with tomato seedlings (Ponte Rosa variety) and cultivated in a greenhouse for 20 days. The suspension containing the test compound corresponding to the formulation of Example 2 is diluted with water to the intended concentration and the resulting solution is carefully sprayed over seedlings at the stage of development of 2-3 leaves of the test plants. Phytophthora infestans spores in the suspension was inoculated on the test plants distribution, which was allowed to stand at ²⁰ ° C overnight in a humid environment. The test plants are additionally grown for 5 days under lighting and observation. The results are shown in table. nine.

 Test example 31. The healing effect against damage to tomato plants, characterized by wilting them and falling leaves without rotting (caused by Phytophthora infestans fungi).

A plastic baking sheet is filled with sandy soil and planted with tomato seedlings (Ponte Rosa variety) and cultivated in a greenhouse for 20 days. Phytophthora infestans spores in the suspension was inoculated on seedlings distribution development stage of 2-3 leaves of the test plants, which was then allowed to stand at 20 ° ^C overnight in a humid environment. A suspension containing the test compound corresponding to the formulation of Example 2 is diluted with water to the intended concentration and the resulting solution is carefully sprayed over the test plants. They are additionally grown for 5 days under lighting and observation. The results are shown in table. nine.

 Test Example 32. Preventive effect against downy mildew (vine) caused by Plasmopara viticola.

 The plastic baking sheet is filled with sandy soil and planted with vine seeds (Berry-A variety), followed by cultivation in the greenhouse for 50 days.

A suspension containing the test compound corresponding to the formulation of Example 2 is diluted with water to the intended concentration and the resulting solution is carefully sprayed on seedlings at the developmental stage of 6-7 leaves of test plants. Plasmopara viticola spores in the suspension was inoculated by spreading them on the test plants, which were then allowed to stand at ²⁰ ° C overnight in a humid environment. The test plants are additionally grown for 8 days under lighting and observation. The results are shown in table. nine.

 Test Example 33. Healing effect on downy mildew (mildew) of grapes caused by Plasmopara viticola.

A plastic baking sheet is filled with sandy soil and seedlings of vines (cultivar Berry-A) are planted there, followed by cultivation in a greenhouse for 50 days. Plasmopara viticola spore suspension is inoculated by distributing from seedlings of test plants at the developmental stage from 6 to 7 leaves. Then, these plants are allowed to stand at 20 ° ^C overnight in a humid environment. The test compound in the composition of the powders corresponding to the formulation of example 3 is dissolved in water and diluted to the intended concentration. The test solution was thoroughly sprayed with the obtained solution from the outside of the test plants, and they were additionally grown for 8 days under lighting and observation. The results are shown in table. 8.

 Test Example 34. Preventing action on downy mildew (mildew) of cucumbers caused by Pseudoperonospora cubensis.

The plastic baking sheet is filled with sandy soil and cucumber seedlings are planted there (Sagamihanjiro variety), after which they are cultivated in the greenhouse for 14 days. The test compound in the suspension according to the formulation of Example 2 is dissolved in water and diluted to the intended concentration. The resulting solution is thoroughly sprayed outside the seedlings of the test plants. Then, spores of Pseudoperonospora cubensis, located in the suspension were inoculated by distributing them on the test plants, which was allowed to stand at ²⁰ ° C overnight in a humid environment. The test plants are additionally grown for 5 days under lighting and observation. The results are shown in table. nine.

 Test Example 35. Healing effect against downy mildew of cucumbers caused by Pseudoperonospora cubensis.

A plastic baking sheet is filled with sandy soil and sown with cucumber seeds (Sagamihanjiro variety), followed by cultivation in the greenhouse for 14 days. Spores in suspension Pseudoperonospora cubensis was inoculated by spreading on the seedlings of the test plants, which were then allowed to stand at ²⁰ ° C overnight in a humid environment. A suspension containing the test compound corresponding to the formulation of Example 2 is diluted with water to the intended concentration and the test plants are thoroughly sprayed with the resulting solution. These plants are additionally grown for 8 days under lighting and observation. The results are shown in table. nine.

 In order to further confirm the advantages of the proposed compounds, the following tests were carried out.

Указанное соединение в общих чертах описано в авт. св. СССР N 270632.Test compound:
The following compounds were used for comparison:
Compound G: CH

The specified connection in General terms is described in ed. St. USSR N 270632.

Указанное соединение конкретно описано в авт. св. СССР N 270632.Compound H: H ₂ N

The specified connection is specifically described in ed. St. USSR N 270632.

 Test method and results.

 Healing effect on cucumbers affected by downy mildew (Pseudoperonospora cubensis).

 The tests were carried out by the method described in test example 8. The test results are presented in table. 10.

 Soil analysis for phytosporosis of tomatoes (Phytophthora infestans).

 The tests were carried out by the method described in example 9. The test results are presented in table. eleven.

 Thus, from all the data presented it clearly follows that all of the proposed compounds are significantly superior in properties to known compounds. Only compound C is at the level proposed by antifungal activity. However, from the data table. 5 shows that at a dose of 500 ppm Compound C exhibits significant phytotoxicity, while the compounds of the invention do not exhibit phytotoxicity even at a dose of 1000 ppm. and so on superior to the known safety compound for crops.

Claims (2)

1. AMIDA DERIVATIVES OF FORMULA I

where R ₁ and R _{2 are the} same or different and each hydrogen or a C ₁ C ₃ alkyl group;
R _{3 is a} 2-furyl group, a 3-furyl group, a 2-thionyl group or a 3-thienyl group. 2. The amide derivatives of claim 1, wherein R ₁ and R _{2 are} each methyl group. Priority by signs:
03/23/88 according to claim 1;
05.26.87 according to claim 2.

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