CS264282B2 - Fungicide agent and preparation method for actives compounds - Google Patents

Abstract

1. A 7-aminoazolo[1,5-a]pyrimidine of the formula I see diagramm : EP0215382,P11,F1 where R**1 is di-C1 -C10 -alkylamino-C2 -C6 -alkyl phenoxy-C2 -C6 -alkoxy-C2 -C6 -alkyl or, in which the phenyl moiety is unsubstituted or monosubstituted or polysubstituted by straight-chain or branched C1 -C10 -alkyl, phenyl, C1 -C10 -alkoxy, phenoxy, halogen, phenyl-C1 -C4 -alkyl, phenyl-C1 -C4 -alkoxy, di-C1 -C10 -alkylamino or C1 -C10 -alkylphenylamino, R**2 and R**3 are each hydrogen or C1 -C4 -alkyl, and A is =N-, =CH-, =C(C1 -C4 -alkyl)-, =CBR- or =CCl.

Description

(57) A fungicidal composition, characterized in that it contains at least one 7-aminoazolo [1,5-a] pyrimidine of the general formula I as an active ingredient, in which R ¹ represents phenyloxyethylenoxypropylene with an optionally substituted phenyl radical or C 1 -C 6 -alkoxy- C 1 -C 1 -alkyleneoxy-C 1 -C 1 -alkylenoxypropylene or di-C 1 -C 6 -alkylamino-C 1 -C 4 -alkylene, R ² is C 1 -C 6 -alkyl, R ³ is hydrogen or C 1 -C 1 -alkyl and A is CH or N , together with a solid or liquid carrier. Further described is a process for the preparation of compounds of the formula I, which comprises reacting the appropriately substituted α-acylnitriles of the formula IV in reaction with aminoazoles of the formula II, optionally in the presence of a solvent.

CS 264 282 B2

The present invention relates to a fungicidal composition comprising the novel 7-aminoazolo [1,5-a] pyrimidines as active ingredient. The invention further relates to a process for the preparation of these novel 7-aminoazolo [1,5-a] pyrimidines.

It is already known that 7-aminoazolo [1,5-a] pyrimidines, in particular 7-amino-6-phenyl-5-methyl [1,2,4] triazolo [1,5-a] pyrimidine, have pharmacological properties ( cf. U.S. Patent No. 2,553,500).

It is further known that 7-aminoazolo [1,5-a] pyrimidines, in particular 7-amino-6- (4-tert-butyloxy-1-butyl) -5-methyl-2-methylpyrazolo [1,5-a] pyrimidine, they can be used as fungicidally active substances (cf. European Patent Specification No. 141317). However, the fungicidal effect of these compounds is not sufficient.

It has now been found that the novel special 7-aminoazolo [1,5-a] pyrimidines of formula I

NHo

R ¹ 1

N ^A (0 in which

R ¹ represents a phenyloxyethylenopropylene group, the phenyl residue being optionally substituted at least once by a halogen atom or an alkyl group of up to 8 carbon atoms; or represents an alkoxyalkyleneoxyalkyleneoxypyropylene group having 1 to 4 carbon atoms in the alkoxy moiety and having 1 to 4 carbon atoms in both alkyleneoxy groups; or represents a dialkylaminoalkylene group having 1 to 6 carbon atoms in the alkyl moieties and having 1 to 4 carbon atoms in the alkylene moiety,

R ² represents an alkyl group having 1 to 4 carbon atoms,

R ³ represents hydrogen or allkylovou group having 1 to 4 carbon atoms,

A is CH or N, in their fungicidal action, they exceed the known compounds, in particular with respect to Odmycetes.

Accordingly, the present invention provides a fungicidal composition, characterized in that it contains at least one 7-aminoazolo [1,5- a] pyrimidine of the formula I as defined above together with a solid or liquid carrier.

The present invention also encompasses a process for the preparation of the novel 7-amino [1,5-a] pyrimidines of formula (I), which comprises:

R ¹ = CH-CN

C = O

AND

R ² (IV 'in which

R ¹ and R ² have the above meanings, is reacted with the formula III aminoazolo

(III) wherein A and R ³ are as defined above, optionally in the presence of a solvent.

The realization of compounds of formula IV with aminoazoles of formula III can be carried out in the presence or absence of solvents. Suitable solvents are, in particular, alcohols, such as ethanol, propanols, butanols, glycols or glycol monoethers, diethylene glycols or their monoethers, amides such as dimethylformamide, diethylformamide, dibutylformamide, N, N-dimethylacetamide, lower alkanesulfonic acids, such as formic acid. acid, acetic acid, propionic acid, and mixtures of these solvents with water. The reaction temperature is between 50 and 300 ° C, preferably between 50 and 150 ° C when working in solution.

In this procedure, the new 7-aminoazolo [1,5-a] pyrimidines are obtained directly. The reaction products are isolated, optionally after evaporation of the solvent or after dilution with water, as crystalline, mostly very pure compounds. When using lower alkanoic acids (fatty acids) as a solvent, it is expedient, if necessary after partial evaporation of the excess, to neutralize the acid residues.

The substituted N-acylnitriles of formula IV which are required as starting materials for the preparation of 7-aminoazolo [1,5-a] pyrimidines are partially known compounds. In individual cases, such novel nitriles may be prepared by known methods from nitriles having a hydrogen position and carboxylic acid esters with strong bases, for example alkali metal hydrides, alkali metal amides or metal alkyl derivatives (cf. J. Amer. Chem.). Soc., 73, [1951], p.

In addition to the process according to the invention, the compounds of the formula I can also be prepared by reacting the appropriately substituted.

in which

R ¹ and R ² have the above meanings, and

R ⁵ represents a lower alkyl group, reacted with an appropriately substituted aminoazole of formula III

in which

A and R ³ have the above meanings, to form the condensation products of the general formula V

R ¹ , R ² , R ³ and A are as defined above, and these are halogenated at the hydroxy group and are also reacted with ammonia.

The β-ketoesters of formula II can be prepared as described in Organic Synthesis Coli., Vol. 1, p. 248, or in DOS 3,227,388. The reaction of these compounds (condensation) with aminoazoles of formula III can be carried out in the presence or absence of solvents. Suitable solvents are, in particular, alcohols such as ethanol, propanols, butanols, glycols or glycol monoethers, diethylene glycols or their monoethers, amides such as dimethylformamide, diethylformamide, dibutylformamide, Ν, Ν-dimethylacetamide, lower alkanesulfonic acids, malic formic acid, acetic acid, propionic acid, as well as mixtures of these solvents with water. The reaction temperature is between 50 ° C and 300 ° C, preferably between 50 ° C and 150 ° C, when working in solution.

The condensation products are generally formed in pure form and after washing, for example with the same solvent or water, and after drying, they are halogenated, for example, with phosphorus halides, preferably at 50 to 150 ^° C in excess phosphorus oxychloride, at reflux. . The base, for example N, N-dimethylaniline, may be added in stoichiometric amounts or in excess. After evaporation of the excess phosphorus oxychloride, the residue is treated with ice water, optionally with the addition of a solvent which is not miscible with water, and the base is optionally removed by extraction with hydrochloric acid.

The chlorination product thus obtained is generally very pure and is therefore reported immediately in reaction with ammonia to give 7-aminoazolo [1,5-a] pyrimidines. This reaction is preferably carried out using a 1- to 10 molar excess of ammonia under pressure (up to 10 bar) at temperatures from about 100 ° C and optionally in a solvent.

The new 7-aminoazolo [1,5-a] pyrimidines are crystalline compounds which are immediately formed in well pure form.

The following examples illustrate the preparation of the active ingredients in more detail.

Example 1

7-Amino-5-methyl-6- [3- [2- (2,4,6-trichlorophenoxy) -1-ethoxy] -1-propyl] [1,2,4] triazolo [1,5-a] pyrimidine (Example 4 of Table 1)

a) Nitrile 2-acetyl-5- [2- (2,4,6-

(trifluorophenoxy) -1-ethoxy] valeric acid

245 g (760 mmol) of 5- (2- (2,4,6-trichlorophenoxy) -1-ethoxy) valeric acid nitrile are dissolved in 1 liter of absolute tetrahydrofuran and cooled to -68 ° C under a protective gas atmosphere. 572 ml of a 1.5 M solution of n-butyllithium in n-hexane (corresponding to 858 mmol of n-butyllithium) are added dropwise over 3 hours, and the reaction mixture is stirred for a further 3 hours at -60 [deg.] C. 0 ml (66.7 g; 758 mmol) of absolute ethyl acetate in 200 ml of absolute tetrahydrofuran The reaction mixture was again allowed to stand at -60 ° C for 3 hours and then allowed to warm to room temperature overnight. The organic phase was separated, washed with water, dried and concentrated to give 267 g of a yellow oil as a residue (73% yield of crude product). ), which can be used for the reaction of step b) without further purification.

(b) Active substance corresponding to the compound of Example 4 of Table 1

All the amount (732 mmol) of the α-acetylnitrile described above is maintained with 61.5 g (731 mmol) of 3-amino-1H-1,2,4-triazole in 1.0 liter of boiling propionic acid for 24 hours. The reaction mixture was then allowed to cool, filtered and concentrated. The residue is taken up in methylene chloride, washed several times with water until the aqueous phase reacts neutrally, dried and evaporated. 166 g [53% (based on the nitrile used as intermediate) of the crystalline material, m.p. 193 DEG-194 DEG C., are thus obtained.

The compounds described in more detail in the following tables (melting point, etc.) were prepared according to the procedures described above. Unspecified compounds can be easily obtained with appropriate variations of the raw materials and with adaptation of the manufacturing regulations. Due to their structural form, a comparable effect of these compounds is expected.

TABLE la

Number (Rn) —X— Melting point ( ^С С) 1 H —ОН (СНз) СНг— 2 н - (СНг) З— 157 to 158 3 2,4,6-С1з —СН (СНз) СНг— 4 2,4,6-013 -1СН ₂ ) 3— 5 2-C1 —СН (СНз) СН2— 6 2-C1 - (СНг) з— 7 4-C1 —СН (СНз) СНг— 8 4-C1 - '(СНг) З— 9 3-C1 —СН (СНз) СН2- 10 3-C1 - (СН2) 3— 135 to 137 11 2-Br —СН (СНз) СНг— 12 2-Br - (СНг) З— 161 to 163 13 4-Br —СН (СНз) СН2— 14 4-Br - (СНг) З— 15 Dec 2-СНз —СН (СНз) СНг— 16 2-СНз - (СН2) 3— 164 to 166 17 3-СНз —СН (СНз) СНг— 18 3-СНз - (СНг) з— 147 to 149 19 Dec 4-СНз —ОН (СНз) СНг— 20 May 4-СНз - (СНг) з— 155 to 158 21 2,4,6- (СНз) з —СН (СНз) СНг— i22 2,4,6- (СНз) з - (СНг) з— 190 to 191 23 t-CdHg — СН2 — С (СНз) 2 —СН (СНз) СНг— 24 terc.CdHg — СНг — С (СНз) 2 - (СНг) з— 25 4-01-2-СНз - (СНг) з— 144 to 145 .26 2- (1-S7) - (СНг) з— 27 Mar: 2- (sec.-CdH9) - (СНг) з— 118 to 120

TABLE lb

Number (R _n ) —X— Melting point ( ^C C)

1-CH2-СШ9 С (СНз) 2 - (CHZ) 3- ^_ '60

TABLE 2 ··. · NH _Z

Number R —X— Melting point ( ^С С) 29 n-H9C'4-O- [CH2) 3- —СН (СНЗ) СН2— resin 30 П-Н9С4 — О— (СНг) 3— - (СН2) 3— 31 П-Н9С4— О— (СН2) 2— —СН (СНз) СН ₂ - TABLE 3

Number

R5

п-СбН1з—

Whose

R ⁴ п-СбН13—

TABLE 4

Number R ² R ³

СНз СНз

СНз СНз

А

N сн

Melting point (° C)

139 to 140

Melting point (° С)

284282

The new active compounds have a strong fungitoxic activity against phytopathogenic fungi, in particular from the class of Phycomycetes.

The novel compounds are therefore suitable for example for controlling potato late blight (Phytophthora infestans) on tomatoes and potatoes, further on Phytophthora parasitica on strawberry, Phytophthora cactorum on apple, Pseudoperenospora cubensis on cucumber, Pseudoperenospora humuli on hops, destructive fungi Peronospora sparsa on roses, perenospora tobacco (Peronospora tabacina) on tobacco, peronospora grapevine (Plasmopara viticola) on grapevine, sunflower mold (Plasmopara halstedii) on sunflowers, Sclerospora macrospora on maize (Mucoea muco) on fruit tree fruits, Rhizopus nigricans on beets, and powdery mildew (Erysiphe graminis) on cereals, grape powdery mildew (Uncinula necator) on grapevine, apple mildew (Podosphaera leucotricha) on apple trees, Sphaerotheca fuliginea on cucumber roses.

The active substances are well tolerated by plants. Some of the active ingredients have curative properties, i.e. the compositions can be used after the plant has been infected with the disease agent in order to achieve a safe result in combating the fungus.

The fungicidal compositions contain from 0.1 to 95% by weight of active compound, preferably from 0.5 to 90% by weight of active compound. Depending on the type of effect desired, the application rate of active substances varies between 0.1 and 5 kg of active substance per ha.

The active compounds can be mixed and co-applied with other active compounds, for example with herbicides, insecticides, growth regulators and other fungicides, or also with fertilizers. In many cases, when mixed with fungicides, the spectrum of fungicidal effect is broadened. Many of these fungicidal compositions also exhibit synergistic effects, i.e. the fungicidal activity of the combined product is higher than the sum of the individual components.

Fungicides which may be combined with the compounds of the invention are, for example, the following compounds:

sulfur, dithiocarbamates and their derivatives, such as dimethyldimethyldithiokarbamát ferric dimethyldithiocarbamate, zinc ethylene-bis-dithiocarbamate, zinc ethylene-bis-dithiocarbamate, manganese ethylene-bis-dithiocarbamate, manganese zinc tetramethylthiurandisulfid, amonikální complex of N, N-ethylene-bis- ⁴ zinc dithiocarbamate, ammoniacal complex of N, N'-propylene-bis-dithiocarbamate zinc,

Zinc N, N‘-propylene-bis-dithiocarbamate,

N, N‘-polypropylene-bis- (thiocarbamoyl) disulfide;

nitro derivatives, such as dinitro (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethyl acrylate,

2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, 5-nitroisophthalic acid diisopropyl ester;

heterocyclic compounds such as

2-Heptadecyl-2-imidazoline acetate

2,4-dichloro-6- (o-chloroanilino) -s-triazine,

O, O-diethylphthalimidophosphonothioate, 5-amino-1- [bis- (dimethylamino) phosphinyl] -3-phenyl-1,2,4-triazole,

2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithio- [4,5-b] quinoxaline, 1- [butylcarbamoyl) -2-

-benzimidazolecarbamic acids,

2-methoxycarbonylaminobenzimidazole,

2- (2-furyl) benzimidazole,

2- (thiazol-4-yl) benzimidazole

N- (1,1,2,2-tetrachloroethylthio) tetrahydrophthalimide,

N-trichloromethylthiophthalimide, N-dichlorofluoromethylthio-N‘, N‘-dimethyl-N-phenyldiamide sulfuric acid, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-rhodanomethylthiobenzthiazole,

1,4-dichloro-2,5-dimethoxybenzene,

4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thio-1-oxide, 8-hydroxyquinoline or its copper salt,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine-4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxylic acid anilide, 2-methylfuran anilide -3-carboxylic acids, 2,5-dimethylfuran-3-carboxylic acid anilide, 2,4,5-trimethylfuran-3-carboxylic acid anilide, 2,5-dimethylfuran-3-carboxylic acid cyclohexylamide,

2,5-dimethylfuran-3-carboxylic acid N-cyclohexyl-N-methoxyamide, 2-methylbenzoic acid anilide, 2-iodobenzoic acid anilide, N-formyl-N-morpholine-2,2,2-trichlorethylacetal, piperazine-1, 4-Diyl-bis-1- (1,2,2-trichloroethyl) formamide; 1- (3,4-dichloroanilino) -1-formylamino-2,2,2-trichloroethane.

284282

2,5-dimethyl-N-tridecylmorpholine or its salts,

2,6-dimethyl-N'cyclododecylmorpholine or its salts,

N- [3- (p-tert-butylphenyl) -2-methylpropyl] -cis-2,6-dimethylmorpholine,

N- [3- (p-tert-butylphenyl) -2-methylpropyl] piperidine,

1- [2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-ylethyl] -1H-1,2,4-triazole, 1- [2- (2,4-dichlorophenyl) ) -4-n-propyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole,

N- (n-propyl-N- (2,4,6-trichlorophenoxyethyl) -N‘-imidazolylurea,

1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone,

1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanol, α- (2-chlorophenyl) -a- (4 -chlorophenyl) -5-pyrimidine-methanol,

5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis- (p-chlorophenyl) -3-pyrimidine-methanol,

1,2-bis- (3-ethoxycarbonyl-2-thioureido) benzene,

1,2-bis- (3-methoxycarbonyl-2-thioureido) benzene,

2-Cyano-N- (ethylaminocarbonyl) -2-

- (methoxyimino Jacetamide as well as various fungicides, such as dodecylguanidine acetate,

3 '[3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene, DL-methyl-N- (2,6-dimethylphenyl) -N-fur-2-oylalaninate, DL-N methyl ester - (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) alanine,.

N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L-2-aminobutyrolactone,

5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidine,

3- [3,5-dichlorophenyl-5-methyl-5-methoxymethyl] -1,3-oxazolidine-2,4-dione,

3- (3,5-dichlorophenyl) -1-isopropylcarbamoylhydantione,

1,2-Dimethylcyclopropane-1,2-dicarboxylic acid N- (3,5-dichlorophenyl) imide. The naive active substances are used, for example, in the form of direct sprayable solutions, emulsions, also in the form of highly concentrated aqueous, oily or other dispersions, pastes, dusts, scatters, granulates, and applied by spraying, dusting, spreading, coating or watering. The use forms depend entirely on the intended use. As a rule, they are intended to ensure the finest possible distribution of the new active substances.

For the production of directly applicable or after emulsifying water-soluble solutions, emulsions, pastes and oil dispersions, suitable fractions of medium to high boiling mineral oil, such as kerosene or diesel oil, tar oils, etc., as well as vegetable oils, are suitable. animal origin, aliphatic, cyclic or aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone etc. strongly polar solvents such as dimethylfluoramide, dimethylsulfoxide, N-methylpyrrolidone, water, etc.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders, oil dispersions by the addition of water. In order to prepare emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent can be homogenized with wetting agents, adhesives, dispersing agents or emulsifiers in water. However, concentrates may also be prepared which consist of the active ingredient, wetting agent, adhesive, dispersing or emulsifying agent and, optionally, solvent or oil, which are suitable for dilution with water.

Suitable surfactants are the alkali metal, alkaline earth metal or ammonium salts of ligninsulfonic acid, naphthalenesulfonic acid and phenolsulfonic acid and the alkali earth metal salts of dibutylnaphthalenesulfonate and the alkali earth metal, lauryl ether sulfate, allkylarylsulfonates, alkyl sulfates, alkyl sulfonates , alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and sulfonated derivatives of naphthalene with formaldehyde, condensation products of naphthalene or naphthalene polymers with phenolemethylene phenol , ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, condenser the products of ethylene oxide with fatty alcohols, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, laurylalkoholpolyglykoletheracetal, sorbitol esters, lignin, sulfite waste liquors and methylcellulose.

Powders, dusts and dusts can be prepared by mixing or grinding the active ingredients with a pastry carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are, for example, mineral clays such as silica gel, silicic acid, silica gel, silicates, talc, kaolin, attaclay, limestone, chalk, bolus, loess, clay, dolomite, diatomite, calcium sulfate and magnesium sulfate, magnesium oxide, ground plastic

2642 62 masses, fertilizers such as ammonium sulphate, ammonium phosphate, ammonium nitrate, ureas and plant products such as cereal flour, tree bark meal, wood meal and nut shell meal, powdered cellulose and other solid carriers.

The following are examples of such products:

AND.

100 parts by weight of the compound of Example 2 is mixed with 100 parts by weight of N-methyl-2-pyrrolidone to give a solution which is suitable for application as minimal drops.

II.

parts by weight of the compound of Example 4 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the addition product, 8 to 10 moles of ethylene oxide with 1 mole of N-monoethanolamide oleic acid, 5 parts of calcium dodecylbenzenesulfonic acid and 5 parts of the addition product 40 moles of ethylene oxide and 1 mole of castor oil. Pouring this mixture into water and finely distributing it in water yields an aqueous dispersion.

III.

parts by weight of the compound of Example 10 are dissolved in a mixture consisting of 30 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the addition product, 40 moles of ethylene oxide with 1 mole of castor oil. Pouring and finely distributing in water gives an aqueous dispersion.

IV.

parts by weight of the compound of Example 16 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction boiling at 210 DEG-280 DEG C. and 10 parts by weight of an adduct of 40 moles of ethylene oxide with 1 mol of castor oil. Pouring and finely distributing the solution in water gives an aqueous dispersion.

IN.

parts by weight of the compound of Example 18 are mixed well with 3 parts by weight of diisobutylnaphthalene-α-sulfonic acid sodium salt, 17 parts by weight of lignin sulphonic acid sodium salt from sulphite waste liquors and 60 parts by weight of silica silicagel powder and ground in a hammer mill. By finely distributing this mixture in water, a spray suspension is obtained.

VI.

parts by weight of the compound of Example 28 are intimately mixed with 95 parts by weight of finely dispersed kaolin. In this way, a dust containing 5% by weight of the active ingredient is obtained.

*

VII.

parts by weight of the compound of Example 29 are intimately mixed with a mixture of 92 parts of powdered silica gel and 8 parts by weight of paraffin oil, which mixture is sprayed onto the surface of the silica gel. In this way, an effective formulation with good adhesion is obtained.

VIII.

40 parts by weight of the compound of Example 32 are intimately mixed with 30 parts by weight of the sodium salt of the condensation product of phenolsulfonic acid, urea and formaldehyde, 2 parts by weight of silica gel and 48 parts of water. A stable aqueous dispersion is thus obtained. Dilution with water gives an aqueous dispersion.

IX

parts by weight of the compound of Example 10 are intimately mixed with 2 parts by weight of calcium dodecylbenzenesulfonic acid, 8 parts by weight of polyglycol ether of fatty alcohol, 2 parts by weight of sodium salt of phenolsulfonic acid, urea and formaldehyde condensation product and 68 parts by weight of paraffinic mineral oil. In this way a stable oil dispersion is obtained.

The following experiments illustrate the biological effect of the novel compounds. Known active ingredients, i.e. 7-amino-6-phenyl-5-methyl- [1,2,4] -triazolo [1,5-a] pyrimidine (A) (a compound known from U.S. Pat. No. 2,553,500) and 7-amino-6- (4-tert-butyloxy) -5-methyl-2-methylpyrazolo [1,5- a] pyrimidine (B) (a compound known from European Patent Specification 141317).

Experiment 1

Effect against peronospora of grapevine (Plasmopara viticola)

The leaves in pots of the grapevine species "Muller-Thurgau" are sprayed with an aqueous suspension containing, in the dry state, 80% of the active ingredient and a 20% emulsifier. In order to assess the duration of action of the active substances, the pots were placed in the greenhouse for 10 days after the spray coating had dried. Only then the leaves are infected with a zoospore suspension of the peronospore of the vine (Plasmopara viticola). Then the plants are first placed in a chamber of saturated water vapor at 24 ° C for 16 hours and then in a greenhouse for 8 days, where they are kept at temperatures between 20 and 30 ° C. After this time, the plants were again placed in a moist icomore for 16 hours to accelerate the penetration of sporangia carriers. The degree of fungal infestation on the undersides of the leaves is then evaluated.

The result of the experiment shows that, for example, using the active substances of Examples 2, 4, 10, 16, 18, 28, 29 and 32 in the form of a 0.05% active substance suspension, a better fungicidal effect (e.g. 97%) is obtained use of known active ingredients (A) and (B) (e.g. 60%).

The results of the test are summarized in the following table, in which 0 means that there was no fungal infestation and in gradual order up to 5 staiv when the fungal infestation was complete.

TABLE

Effective Leaf attack after treatment with substance number 0.05% with the preparation of the active substance. 21

101

161

180

281

291

321 Comparison product A3 Comparison product В3—4 untreated5

The leaves in pots of tomato plants of the "GroRe Fleischtomate" species are sprayed with an aqueous suspension which contains 80% active ingredient and 20% emulsifier in the dry matter. After the spray layer has dried, the leaves are infected with a zoospore suspension of fungal fungi (Phytophthora infestans j. The plants are then left in a chamber saturated with water vapor at temperatures of 16-18 ^° C. After 5 days, the disease develops to untreated but infected control plants. The fungicidal activity of the test substances can be assessed.

The result of the experiment shows that, for example, using the active compounds of Examples 4, 27 and 32 in the form of a 0.025% active substance spray suspension, a better fungicidal effect (e.g. 97%) is obtained than using the known active compound В (0%).

The results of this locus are summarized in the following table, in which the degree of infestation is expressed by numbers from 0 to 5, where 0 means no fungal attack and 5 means complete fungal attack.

Claims (2)

TABLE Effective Leaf attack substance number after treatment with 0.025% active substance preparation 270 321 Comparison product В6 untreated5 Experiment 2 Effect against potato late blight (Phytohthora infestans) on tomatoes A fungicidal composition, characterized in that it contains at least one 7-aminoazolo [1,5-a] pyrimidine of the formula I as active ingredient VYNALEZU R ¹ represents a phenyloxyethyleneoxypropylene group, wherein the phenyl moiety is optionally substituted at least once with a halogen atom or a C 1 -C 8 alkyl group; or is (C1-C4) alkoxyalkyleneoxyalkyleneoxypropylene or (C1-C4) alkoxy in both alkyleneoxy groups; or represents a dialkylaminoalkylene group having 1 to 6 carbon atoms in the alkyl moieties and having 1 to 4 carbon atoms in the alkylene moiety, R ² represents an alkyl group having 1 to 4 carbon atoms, R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, A is CH or N in which they react with aminoazoles of formula III 1S together with a solid or liquid carrier. 2. A method for producing an active ingredient according to claim 1 of formula I wherein _R, the appropriately substituted a-acyl nitrile of formula IV R1-CH-CN I c = o AND R ² (IV) wherein R ¹ and R ² are as defined in (1) (III) in which: A < ³ > and R < ³ & gt ^; are as defined in 1, optionally in the presence of a solvent.