CS215060B2 - Fungicide means - Google Patents

Abstract

1. Claims for the Contracting States : BE, CH, LI, DE, FR, GB, IT, LU, NL, SE A 2-(N-aryl-n-acyl)-aminopropanal-acetal of the general formula I see diagramm : EP0019745,P23,F3 where X**1 , X**2 and X**3 independently of one another are oxygen or sulfur, Y is oxygen, sulfur or NR**7 , n is 0 or 1, R**1 is C1 -C4 -alkyl, R**2 is hydrogen, halogen, C1 -CV4 -alkyl or C1 -C4 -alkoxy, R**3 is hydrogen, halogen or C1 -C4 -alkyl, R**4 and R**5 independently of one another are unsubstituted or substituted alkyl or arylalkyl or together are alkylene and form part of a 5-membered or 6-membered heterocyclic ring which may or may not be substituted by alkyl or aryl, R**6 is unsubstituted or substituted alkyl, alkenyl, cycloalkyl, cycloalkenyl or heteroaryl, with the exception of chloromethyl and acetylmethyl, and if n is 1, R**6 may also be unsubstituted or substituted alkynyl, aryl, arylalkyl or heteroarylalkyl, and R**7 is hydrogen, alkyl or alkoxy. 1. Claims for the Contracting State : AT A fungicide containing a 2-(N-aryl-n-acyl)-aminopropanalacetal of the formula see diagramm : EP0019745,P27,F1 where X**1 , X**2 , and X**2 independently of one another are oxygen or sulfur, Y is oxygen, sulfur or NR**7 , n is 0 or 1, R**1 is C1 -C4 -alkyl, R**2 is hydrogen, halogen, C1 -C4 -alkyl or C1 -C4 -alkoxy, R**3 is hydrogen, halogen or C1 -C4 -alkyl, R**4 and R**5 independently of one another are unsubstituted or substituted alkyl or arylalkyl or together are alkylene and form part of a 5-membered or 6-membered heterocyclic ring which may or may not be substituted by alkyl or aryl, R**6 is unsubstituted or substituted alkyl, alkenyl, cycloalkyl, cycloalkenyl or heteroaryl, with the exception of chloromethyl and acetylmethyl, and if n is 1, R**6 may also be unsubstituted or substituted alkynyl, aryl, arylalkyl or heteroarylalkyl, and R**7 is hydrogen, alkyl or alkoxy.

Description

The present invention relates to novel 2- (N-aryl-, N-acyl) -amino-propmalacetals, to a process for their preparation, to their use as fungicides in a process for the preparation of substituted anilines.

It is well known that N-trichloromethylthiotetrchidrophimide is a good feature for combating fungal diseases in plants, especially for the control of false powdery mildew on grapevines (Chenmcel).

Week 19'72, 21 June, p. 63). However, the effect of this substance on other Plhycomcetes fungi, such as Phytophthora infestans, on tomatoes or potatoes is not satisfactory. It is furthermore known that sub-induced 1,3-diklan-2-ylmethyl groups carrying a 1,3-dichloro-acetyl group exhibit herbicidal activity (cf. DOS No. 2 405 5Ю).

It has now been found that the novel 2- (N-aarl-, N-acyO-eminopropaneacetels of formula I)

R ⁴ R ⁵

(AND)

O in which

AND? is C1-C4alkyl, o

R ^& is hydrogen, halogen or alkylevou group having 1 Al 4 C atoms,

R ⁴ and ar are independently C 1 -C 4 alkyl or together form a methylene chain containing 2 or 3 methylene groups, optionally substituted with methyl or phenyl; and

R 6 represents a methyl group, optionally substituted by a methoxy group, an ethoxy group, an ethoxy group, a triacetyl or an imidazole moiety, or represents a cyclopropyl group, having potent fungicidal properties.

In formula I, an alkyl group having 1 to 4 carbon atoms is as defined

2

R is, for example, metal, ethyl, i-pycyl, isopropyl or butyl. R represents a hydrogen atom, a halogen atom, for example fluorine, chlorine or bromine, or an alkyl group having 1 to 4 carbon atoms, for example a methyl, ethyl, propyl or butyl group.

Alkyl groups having 1 to 4 carbon uU.íOu ai represented by the symbols R ⁴ and R ⁵ may be straight or branched and examples include radical meetylovou, ethyl, n-propyl, iscprcpylcvou, Nb-yl, or IS-learner ^^.

The new 2- (N-ayl, N-acyl) amino-prophylactic content of the carbon atom at the 2-position of the propanal portion of centaim asymmetry and, depending on the nature of the R symbol, may contain additional amounts asymmetric. Optically pure enantiomers or diastereomers can be obtained by methods. The invention. these compounds will also be included. Both the pure enantiomers or the uniform diastereomers and the mixtures of the individual conducting isomers can be used as fungicides, as are usually formed in the preparation of these compounds.

Anilines of formula II

in which

R ^1, R ^2, R ^ and R ^ are as defined above required for the preparation of the novel compounds are known. So M. Chastrette [Ann. Chim. (Paris) 2, 643-668 (1962)] described the synthesis of 2- (N-2'-methylphenyl) aminopropanaldiethylacetal (ibid., Page 654, Table II, 4th row) by reaction of 2-bromopropenaldiethylacetal with 2-methylaniline (ibid. 656, 657t yield 24%) or by reaction of methylmagnesium iodide with N-phenyliminoglyoxyldiethylacetal (ibid., p. 658; yield 72%) ·

Furthermore, a portion of the anilines of the general formula II which are used as starting materials is the subject of DOS No. 2,802,211. In this publication, it describes aniline with a cyclic acetal structure, namely 2- (N-2-methyl-6-ethylphenyl) aminopropanal-ethylene glycol acetal.

It has now been found that the anilines of formula XII

(XII) in which

2

R and R are as defined above and

10

R @ 1 and R @ 2 each independently represent a C1 -C4 alkyl group, preferably obtained by the use of methyl glyoxalacetal of the formula XIII

(XIII) ^X 1 -R ¹⁰ is reacted with an aniline of formula XIV *

(XIV) and the resulting Schiff base is hydrogenated, for example by treatment with complex hydrides or catalytically.

- - 10 10

In the general formula (XII), R R represents straight-chain or branched alkyl groups containing up to 4 carbon atoms, for example, meetyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl.

In the process according to the invention, the formation of inorganic salts formed in large scale as by-products in the known reaction of halopropaneacetals and amines in which they are formed by reacting the liberating halogen with inorganic auxiliary bases can be avoided. In addition, the new process is easier to carry out, since it does not have to be carried out under the absolute dry reaction conditions required in the known Grignard reactions. The process according to the invention is therefore simpler and more environmentally friendly than the known processes.

A further advantage of the novel process is that amines of the formula XII can be obtained on a larger scale than the laboratory scale by the following process:

and

1. Preparation of the base salts of formula XV

R ⁹

R ¹ ° (XV) by heating the reaction network to boiling - under a reflux condenser to remove water, and

2. the successor to hydrogenation.

The first reaction step, i.e. the preparation of the scf base bases, is carried out, for example, by reacting 1 mooaniline of the formula (XIV) with 0.9 to 1.5 moles of methylglyoxalalethyl of the formula (XIII) in a solvent, optionally with the addition of a catalyst. wherein the reaction is carried out at a temperature of from 40 to 200 ° C, preferably from 50 to 120 ° C, under pressure or under hook, continuously or discontinuously. Suitably, inert solvents are used under these reaction conditions. Examples of such solvents are:

aromatic hydrocarbons such as benzene, toluene, ethylbenzene, o-, m-, p-xylene, isopropylbenzene or οθΙΙΙποΙΙι ^ ο, aliphatic or -cyccooliphatic hydrocarbons such as heptene, pinane, nonane, gasoline fractions from 70 to 70 190 DEG C., cyclohexane, Mettu ^r lcylcloUexan, dekkHn, hexane, ligroin, 2,2,4-trimetUylpentln, 2,2,3-trimethyl-yrlpeotlo, 2,3,3-trimethylpentane and octane, as well as those odpooUdθljcí smměi rozpouušědee . Suitably, the solvent is used in an amount of from 150 to 10,000% by weight, preferably from 300 to 600% by weight, based on the starting material of the formula (XIV).

The above reaction can be carried out as follows:

The mixture of the starting materials of the formulas XIII and XIV and the solvent is kept at a suitable reaction temperature for 2 to 15 hours. Advantageously, some of the water may be continuously removed during the reaction by azeotropic de-distillation with a suitable solvent such as cyclohexane. The base may then be separated from the reaction mixture in a conventional manner, for example by fractionation by distillation, and the second reaction step may be carried out with a purified Schhff base. However, this process is generally not initiated, in particular for economic reasons, but is preferably carried out by separating off the solvent after the addition of a Schüffouy base, adding a solvent suitable for hydrogenation to the residue and then hydrogenating at a temperature of? Xi ^ i ^ j ^ osst ..

Suitable for this hydrogenation are both a reduction with complex hydrides, such as a hydride or a lithium amine hydride, as well as catalytic hydrogenation.

The reduction with sodium borohydride is generally carried out by reacting the Schiff base in a solvent with 0.2 mol to 1 mol, preferably 0.25 to 0.5 mol of sodium borohydride per mol of Schiff base, at a temperature between -20 to +20 ° C, without or under pressure, continuously or discontinuously.

In the catalytic hydrogenation, an amount of hydrogen is initially introduced into the reaction mixture during and during the reaction so as to maintain a corresponding reaction pressure of between 15 and 30 MPa at the chosen reaction temperature. The reaction is generally carried out at a temperature of 20 to 200 ° C, preferably 25 to 160 ° C, batchwise or continuously. Inert gases such as nitrogen may also be used to adjust the pressure.

Suitable solvents for both process variants are those which are inert under the reaction conditions, such as alkanols and cycloalkanols, for example n-butanol, isobutanol, tert-butanol, glycol, glycerine, n-propanol, isopropanol, amyl alcohol, cyclohexene, 2-methyl -4-pentanol, ethylene glycol monoethyl ether, 2-ethylhexanol, methyl glycol and especially ethanol or methanol, and cyclic ethers such as tetrahydrofuran or dioxane. The solvents mentioned above for the description of the first reaction step are also suitable. Preferably, the amounts of solvents mentioned in the description of the first reaction step are used.

For the catalytic hydrogenation, the catalyst is generally used in an amount of 5 to 30% by weight, based on the Schiff base. The catalyst can be used in admixture with a suitable carrier, for example silica, and the amount of catalyst is usually from 10 to 40% by weight, based on the catalyst / carrier mixture.

Suitably, copper chromite catalysts are used, for example the corresponding copper and chromium oxide catalysts, such as copper chromites used by H. Adkins. These catalysts include, for example chromitoměňnatý spinel (euCr ₂ 0 ^) or a mixture of copper oxide and chromium oxide in the ratio of 5 CuO: 4 Cr ₂ 0p optionally based on these compounds and may additionally contain other oxides, in particular oxides of alkaline earth metals such as Ba, Ca or magnesium.

With regard to the preparation of chromo-copper-copper catalysts, reference is made to Houben-Weyl, Methoden der Organischen Chemie, Vol. 4/2, pp. 180-183, and Journal of Applied Chemistry, Vol. 5 (1955), pp. 289-295.

The preparation of the anilines of formula II is illustrated by the following process description:

121 parts (parts by weight) of 2,6-dimethylaniline, 118 parts of methylglyl oxaldimethylacetal and 0.2 parts of p-toluenesulfonic acid are refluxed in 500 parts of cyclohexane for 4 hours until 18 parts of water are distilled off azeotropically from the distillate separates. Then the solvent was distilled off and the residue was directly reacted.

The yield of Schiff base was 212 parts (96%).

Step 2

(a) catalytic hydrogenation

H ₂

A 1000 volume by volume hydrogenation autoclave was charged with 200 parts of Schiff base prepared from 2,6-dimethylaniline and methylglyoxaldimethylecetal dissolved in 500 parts of tetrahydrofuran and 15 parts of Adkins catalyst (cuprous chromite in powder form).

The autoclave is heated to 160 ° C and pressurized to 20 MPa with hydrogen. Once the hydrogen consumption has subsided and the pressure has stabilized at a constant value (after about 7 hours), the reaction mixture is cooled and worked up.

The catalyst was separated from the reaction mixture by filtration, and 129 parts of 2- (N-2,6-dimethylphenyl) aminopropane-1-dimethylacetal were obtained by distillation, b.p. Yield: 64%.

b) sodium borohydride reduction

220 parts of Schiff base prepared from 2,6-dimethylaniline and methylglyoxaldimethylacetal are dissolved in 1000 parts of methanol and 57 parts of sodium borohydride are added portionwise at 0 ° C. The reaction mixture is stirred overnight, then the solvent is distilled off, the residue is dissolved in 1000 parts of water and the solution is extracted four times with 300 parts of methylene chloride each time. After methylene chloride was distilled off, 205 parts of crude product distilling at 81 ° C / 13 Pa were obtained as a residue. The yield of pure product is 182 parts (81%).

The following anilines corresponding to formula XII can be obtained in an analogous manner

Table I

o — CH ₃

R ¹ R ² boiling point (° C / Pa) ^CH 3 H 75/10 ^C 2 ^H 5 H 84/10 CH ₃ ^C 2 ^H 5 86 to 88/10 ^C 2 ^H 5 ^C 2 ^H 5 92 to 93/10 CH ₃ Cl 90 to 92/10

The novel compounds of the formula I can be obtained by reacting the aniline of the formula II

(II) in which

R ¹ , R ² , R ⁴ and R 6 are as defined above, reacted

a) with an acid halide of the formula III

R ⁶ -C -Hal (III) or

b) an acid anhydride of the formula IV ° 6

R 0 -C-O-C-R 0 (IV) or

c) with an isocyanate of the formula V

R ⁶ -N = C = O (V) in which it is as hereinbefore defined, optionally in the presence of a solvent or diluent, optionally with the addition of an inorganic or organic base and optionally with a reaction accelerator, at a temperature between 0 and 120 ° C;

Preferred solvents or diluents include halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane or chlorobenzene, aliphatic or aromatic hydrocarbons such as cyclohexene, petroleum ether, benzene, toluene or xylenes, esters such as ethyl acetate, nitriles such as acetonitrile, sulfoxides , such as dimethylsulfoxide, ketones, such as acetone or methyl ethyl ketone, ethers, such as diethyl ether, tetrahydrofuran or dioxane, or the corresponding mixtures.

Suitably the solvent or diluent is used in an amount of 100 to 2000% by weight, preferably 100 to 1000% by weight, based on the starting materials of the formulas II, III, IV or V respectively.

Suitable inorganic or organic bathes which may also be used as acid binding agents in the reaction are, for example, alkali metal carbonates such as sodium or potassium carbonate, alkali metal hydrides such as sodium hydride, tertiary amines such as trimethylamine, triethylamine, N, N-dimethylaniline , Ν, Ν-dimethylcyclohexylamine,

N-methylpiperidine or pyridine, and azoles such as 1,2,4-triazole or imidazole. However, other conventional bases may also be used for this purpose.

Suitable reaction accelerators are preferably metal halides such as sodium bromide or potassium iodide, azals such as imidazole or 1,2,4-triazole, or pyridines such as

4-dimethylaminopyridine, or a combination of these reaction accelerators.

The described reaction is generally carried out at a temperature between 0 and 120 ° C for 1 to 60 hours, under or under pressure, continuously or discontinuously.

In general, 0.9 to 1.3 mol of the compound of the formula III or IV or V, as well as 0.5 to 2 mol of the base and, if appropriate, 0.01 to 1.3 mol are used per mole of the compound of the formula II. 0.1 mol reaction accelerator.

According to a preferred embodiment of the process according to the invention, the starting material of the formula II is optionally mixed with a base and optionally a diluent, the starting material of the formulas III, IV or V and optionally the reaction accelerator is added, and the reaction mixture is left 0.5 to 12 hours, preferably 1 to 6 hours, to react at a temperature between 0 to 120 ° C.

To isolate the novel compounds, the solvent is optionally evaporated, the residue is dissolved in a suitable solvent and the solution is washed with dilute aqueous acid, then dilute aqueous lye and water to remove excess base and starting materials of formulas II, III, IV and V.

Products remaining after solvent distillation generally do not need any further purification, but can be further purified by known methods such as recrystallization, extraction or chromatography.

Another subgroup of compounds of formula I according to the invention is obtained by providing compounds of formula XI

(XI) wherein r ', R 1, R 1, R 1, and R 10 are as defined above, reacetalize by reaction with 1,2- or 1,3-diols, to form cyclic acetals, at a temperature between 0 and 120 ° C, optionally in the presence of a solvent or diluent and optionally with the addition of a reaction accelerator.

The 1,2-or 1,3-diols mentioned above include, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propahdiol, 2-methyl- or 2-phenyl-1,3-propanediol.

Suitable solvents or diluents are the abovementioned liquids or 1,2- or 1,3-diols when used in stoichiometric amounts or in excess. Suitable reaction accelerators are Lewis acids or protonic acids, for example zinc chloride, aluminum chloride or boron trifluoride or mineral or sulfonic acids. The isolation of the resulting products is carried out by the methods described above.

Further subgroups of the compounds of the formula I according to the invention are obtained by carrying out the usual additional chemical operations, depending on the functional nature of the radicals R @ 1.

The preparation of the novel compounds of the invention is illustrated by the following non-limiting examples.

Example 1

A mixture of 30 parts of 2- (N-2 ', 6'-dimethylphenyl-, N-chloroacetyl) aminopropanal dimethylacetal, 20.4 parts of imidazole, 50 parts of dioxane and 20 parts of water was heated at reflux for 8 hours. After evaporation of the reaction mixture in vacuo, the residue was dissolved in 100 parts of methylene chloride, washed three times with 50 parts of water each time, dried over sodium sulfate and evaporated. After purification of the crude product by filtration of its solution in ethyl acetate over silica gel, 18.1 parts of a uniform oil are isolated.

Analysis:

calculated: C 65.2%, H 7.6%, N 12.6 found: C 64.8%, H 7.8%, N 12.1%.

The following compounds were prepared in an analogous manner:

Table 2

example number teglota boiling; ⁿ D 2 ^CH 3 Cl CH ₂ OCH ₃ 1.5235 3 ^C 2 ^H 5 c ₂ H ₅ CH ₂ -OCH ₃ 143/15 Pa 4 ch ₃ H CH ₂ -OCH ₃ 1.5080 5 CH ₃ Cl CH ₂ OC ₂ H ₄ OCH ₃ 1,5045 6 CH ₃ CH ₃ CH ₂ (OC ₂ H ₄ ) ₂ OCH ₃ 1,4982 7 CH ₃ ^CH 3 CH ₂ OC ₂ H ₄ OCH ₃ 1,4990 8 CH ₃ CH ₃ ен _г - <\ mp 85 ° C

continuation of Table 2

example number R * R ² r " boiling point; '20 ⁿ D 9 CH ₃ CH ₃ CH ₂ —NN w mp 167 ° C 10 CH ₃ CH ₃ 1.5130 11 CH ₃ CH ₃ CH ₃ 1,5076 12 ^CH 3 CH ₃ CH ₂ -O-CH ₃ 1,5071 13 ^CH 3 ^C 2 ^H 5 CH ₂ -O-CH ₃ 140 to 142/20 Pa 14 ^CH 3 ^CH 3 CH ₂ -OC, > ^H 5 oil

The following compounds can be prepared as described above:

R ⁴ R ⁵

Example R 11 ¹ number · + melting point (° C);

ⁿ D

CH ₃ CH ₃

-ch ₂ -ch ₂ ch ₃ ch ₃

-ch ₂ -ch ₂ -

136 to 137

146

CH ₃ ^C 2 ^H 5 • CH ₂ -CH ₂ <

128 to 130

CH ₂ —N — CH ₂ —N

oil ^CH 3

CH ₂ CH ₃

-CH ₂ -CH ₂ -

19 Dec ^CH 3 ^CH 3 -CH ₂ -CH ₂ - -0 82 to 90 20 May ch ₃ ch ₃ -CH ₂ -CH ₂ - CH ₂ -OCH ₃ 1,5255 31 ch ₃ ch ₃ -CH ₂ -C, (CH ₃ ) (C ₈ H ₅ ) -CH ₂ CH ₂ -OCH ₃ 1.5470 22nd ^CH 3 CH ₃ -CH (CH ₃ ) -CH ₂ - CH ₂ -OCH ₃ 1,5182

continued table

example number R ¹ and?- R ⁴ R ⁵ R ⁶ melting point (° C) ⁿ D « - 23 CH ₃ GH ₃ * * CH ₂ -CH ₂ -CH ₂ - CH2 ₂ OCH ₃ 05 to 90 24 CH ₃ ^CH 3 -CH (CH ₃₎ -CH ₂ -CH ₂ - CH ₂ -OCH ₃ 1.4980 25 CH ₃ ^CH 3 -CH (CH ₃₎ -CH (CH ₃₎ - CH ₂ -OCH ₃ 1.5075 26 CH ₃ Cl iCH ₂ -CH ₂ - CH ₂ -OCH ₃ 'д' 1.5298 27 Mar: ^CH 3 ^CH 3 ^С1 Шк ^Н 3? 2 ' ^СН 2 · CH ₂ -OCH _3- '*' 1,5121 20 May CH ₃ H -CH ₂ -CH ₂ - CH ₂ -OCH ₃ oil 29 CH ₃ ^CH 3 -CH ₂ -CH (C ₈ H ₅ ) - CH ₂ -OCH ₃ 1,543 30 CH ₃ Cl -CH ₂ -, C (CH ₃ ) (C ₈ H ₅ ) CH ₂ - CH ₂ -OCH ₃ 1.5448 31 ^CH 3 CH ₃ '-CH ₂ -CH _2X J - - CH ₂ OC ₂ H ₅ 1.5145 32 ^сн з CH ₃ -CH ₂ -CH ₂ - CH ₂ OC ₂ H ₄ OCH ₃ 1.5138

The active compounds according to the invention show a strong fungitoxic effect. Said compounds at the concentrations required to combat fungi and bacteria do not damage crop plants. For these reasons, the compounds can be used as agents for protecting plants against fungal diseases.

The novel active compounds according to the invention show a strong fungitoxic action against phytopathogenic fungi, in particular from the class of Phycomycetes. The compounds according to the invention are therefore suitable, for example, for controlling Phytophthora infestans on tomatoes and potatoes, Phytophthora parasitica on strawberries, Phytophthora cactorum on apples, Pseudoperonospora cubensis on cucumbers, Pseudoperonospora humuli on hops, Peronospora onctul (Peronospora onctulul) sparsa on roses, Peronospora tabacina on tobacco, Plasmopara viticola on grapevine, Plasmopare halstedii on sunflowers, Sclerospora macrospora on corn, Bremia lactucae on mildew fruits, Rhizopus nigricans on beets.

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

Some of the active compounds exhibit curative properties, i.e. the composition can be applied even after infection of the agent by the agent to achieve safe destruction of the causative agent of the fungal disease. In addition, many of the novel compounds are systemically active, allowing the protection of aboveground plant parts by root treatment. In addition, fungi causing diseases of germ and emerging plants, such as Pythium and Aphanomyces species on vetches and broccoli, can also be combated with the novel compounds of the invention. Consumption in this case ranges from 10 to 200 g of active ingredient per 100 kg of seed, the active ingredients being applied in the form of seed dressings.

The compounds of the invention are applied by spraying or dusting the plants with the active compounds or by treating the seeds of the plants with the active compounds. Application is carried out before or after infection of the plants or seeds by the fungus.

The active compounds je.moŽnd converted into the customary formulations, such as solutions, emulsions, sus ^p Enns RAEE ^p o ^{p p ras} memory means, and ^{the p} and ^g Ranuli. The ^application forms are entirely guided by the purposes of use, but in any case are intended to ensure a fine and even distribution of the active ingredient. These are prepared in known manner, for example by mixing-active ^substance with extended ^beta Oust ^ed l ^y and ^/ or carriers, ^^ am ^ ^p o ^or A ^{de surcharge} ou ^fo T ⁱ emulsifier & tors and ^ Žsiergátorů, wherein - when using water organic solvents can also be used as diluents as diluents.

The carrier and auxiliaries which can be used are, in particular, solvents: aromatics (e.g. xylene or benzene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol or butanol), amines (e.g. ethanolamine), dimethylformamide and water; carriers such as natural stone meal (for example kaolins, alumina, talc or chalk) and synthetic stone meal (for example highly disperse silicic acid or silicates); emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin-sulfite waste liquors and methylcellulose.

The concentrates, or compositions which can be prepared therefrom, such as solutions, emulsions, suspensions, powders, dusts, pastes or granules, are applied in a known manner, for example by spraying, fogging, dusting, pickling or dressing.

The following preparations are exemplified by the above compositions:

I. 90 parts by weight of the compound of Example 1 are mixed with 10 parts by weight of N-methyl-.alpha.-pyrrolidone to give a solution which is suitable for application as small droplets.

II. 20 parts by weight of the compound of Example 2 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the editorial product 8 to 10 moles of ethylene oxide per mole of N-monoethanolamide oleic acid, 5 parts by weight of dodecylbenzenesulfonic acid calcium. 40 mole of ethylene oxide per mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

III. 20 parts by weight of the compound of Example 3 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the edition product, 7 moles of ethylene oxide per mole of isooctylphenol and 10 parts by weight of addition product 40 moles of ethylene oxide per mole. castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

IV. 20 parts by weight of the compound of Example 1 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of the fractions of mineral - oil on te ^p ture point of 2 ¹⁰ to ²⁸⁰ ° C, and 10 ^{of i} c ^h says ^profiles adičntao ^p roducts 4 ⁰ mol of ethyl Lenoxide per mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

V. 20 parts by weight of the active compound of Example 2 are mixed well with 3 parts by weight of sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 17 parts by weight of sodium salt of ligninsulfonic acid from waste sulphite lyes and 60 parts by weight of powdered silica gel, and hammer mill. By uniformly distributing the mixture in 20,000 parts of water masses from ⁱ to ^{p ka} ostMkov ^{suspensions. To Ter} otoahuje

0.1% by weight of active ingredient.

VI. 3 parts by weight of the compound of Example 3 are intimately mixed with 97 parts by weight of finely divided kaolin. In this way, a dust containing 3% by weight of the active ingredient is obtained. '

VII. 30 parts by weight of the compound of Example 1 are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been 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 active compound of Example 2 are intimately mixed with 10 parts of sodium salt of the condensation product of phenolsulfonic acid, urea and formaldehyde, 2 parts of silica gel and 48 parts of water to obtain a stable aqueous dispersion. By diluting this dispersion with 100,000 parts by weight of water, an aqueous dispersion containing 0.04% by weight of the active ingredient is prepared.

IX 20 parts of the active ingredient of Example 3 are intimately mixed with 2 parts of calcium dodecylbenzenesulfonic acid, 8 parts of polyglycol ether of fatty alcohol, 2 parts of sodium salt of phenolsulfonic acid, urea and formaldehyde condensation product and 68 parts of paraffinic mineral oil fraction to obtain a stable oil dispersion .

The active compounds according to the invention can be present in these compositions, together with other active substances, such as herbicides, insecticides, growth regulators and fungicides, or they can also be mixed with fertilizers and applied in this form. When mixed with fungicides, in many cases the efficacy spectrum is expanded.

The following list of fungicides with which the compounds of the invention may be combined further illustrates these combination possibilities, but is not intended to limit them in any way.

Fungicides with which the compounds of the invention may be combined are, for example, dithiocarbamates and derivatives thereof, such as ferric dimethyldithiocarbamate, zinc dimethyldithiocarbamate, manganese ethylene-bis-dithiocarbamate, manganatosine amethylenediamethiamine di-ethylenediamine di-ethylenediamine di-ethylenediamine, Zinc Ν, Ν'-ethylene-bis-dithiocarbamate and N, N'-polyethylene-bis-phthiocarbamoyddi sulfide,

Zinc N, N'-propylene-bis-dithiocarbamate, zinc ammoniacal complex of Ν, pr-propylene bis-dithiocarbamate and N, N'-polypropylene-bis- (thiocarbamoyl) di-sulfide, nitroderivatives such as dinitro- (1- methylheptyl) phenylcrotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethyl acrylate, 2-sec-butyl-4,6-dinitrophenylisopropyl carbonate;

heterocyclic compounds such as

N-trichloromethylthio-tetrahydrophthalimide,

N-trichloromethylthio-phthalimide, 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, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole,

2 ₅ 3-dicyano-1,4-dithioanthraquinone,

2-thio-1,3-dithio [4,5-b] quinoxaline, 1-butylcarbemoyl-2-benzimidazolecarbamic acid methyl ester, 2-methoxycarbonylaminobenzimidazole, 2-thiocyanatomethylthiobenzthiazole,

4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thiol-1-oxide,

8-hydroxyquinoline or its copper (II) salt,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine-4,4-dioxide,

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

2- (2-furyl) benzimidazole, piperazine-1,4-diylbis- [1- (2,2,2-trichloroethyl) formamide],

2- (4-thiazolyl) benzimidazole

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

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

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

and various fungicides such as dodecylguanidine acetate,

3- [3- (3,5-dimethyl-2-hydroxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene,

Sulfuric acid N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenyldiamide,

2,5-dimethylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxylic acid cyclohexylamide, 2-methylbenzoic acid anilide, 2-iodobenzoic anilide, 1- (3,4-dichloroanilino) -1-formylamino-2,2, 2-trichloroethane,

2,6-dimethyl-N-tridecylmorpholine and its salts,

2,6-dimethyl-N-cyclododecylmorpholine and its salts, D, L-methyl-N- (2,6-dimethylphenyl) -N-2-furoylalaninate, D, Ь-N- (2,6-dimethylphenyl) -N- methyl ester (2'-methoxyasyl) alanine, 5-nitroisophthalic acid diisopropyl ester,

- (1 ', 2', 4'-triazol-1'-yl) - [1- (4'-chlorophenoxy)] - 3,3-dimethylbutan-2-one, 1- (1 ', 2', 4 1-Triazol-1'-yl) - [1- (4'-chlorophenoxy)] - 3,3-dimethylbutan-2-ol, N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L-2 -aminobutyrolactone, N- (n-propyl) -N- (2,6-trichlorophenoxyethyl) -N'-imidazolylurea, 2,5-dimethylfuran-3-carboxylic acid N-cyclohexyl-N-methoxyamide, anilide 2,4,5 - trimethylfuran-3-carboxylic acids,

5-methyl-5-vinyl-3- (3 5Tdichlorfenyl _R) -2,4-dioxo-1,3-oxazolidine, 5-methoxymethyl-5-methyl-3- (3,5-dichlorophenyl) -2,4- dioxo-1,3-oxazolidine, N- [3- (p-tert-butylphenyl) -2-methylpropyl] -cis-2,6-dimethylmorpholine.

the following compounds are used as known nines in the following tests:

(compound A) known from DOS No. 24 05 510 (compound B) known from Chem · Week 1972, 21.VI., p. 63

Test 1

Fungicidal activity against Phytophthora infestans (potato late blight) on tomatoes

The leaves of tomato plants (Professor Rudloff species) are sprayed with aqueous suspensions containing in the dry state 80% (w / w) of the test substance and 20% of sodium lignin sulphonate. Spray suspensions of 0.025 and 0.012 wt. % (dry matter). After the spray coating has dried, the leaves of the plants are infected with a zoospore suspension of Phytophthora infestans and transferred to a water-saturated chamber where they are kept at 16-18 ° C. After 5 days, the disease develops on untreated infected plants to the extent that the fungicidal activity of the test substances can be evaluated.

The results are shown in the following table, with values from 0 to 5, where 0 means no fungus occurrence and 5 represents complete fungal attack (as in control plants).

active ingredient by attacking the leaves after spraying a suspension containing the active ingredient in a concentration

0.025% 0.012%

1 0 0 2 0 2 4 0 2 8 0 1 9 0 1 19 Dec 0 0 21 0 p 5 1 2 zn; 3 6 1 2 7 1 2 14 0 1 16 1 2 17 0 2 22nd 0 2 23 1 2 24 0 2 to 3 inspection (untreated) 5

T e s t 2

Fungicidal activity against pea plant diseases

Stogram samples of peas (Senator species) were shaken vigorously for about 5 minutes with 300 mg (0.3 wt.%) Of seed dressing containing 40 wt. % active substance. 100 seeds are then sown in separate seeding boxes filled with compost plants naturally infected with the fungi Pythium spec., Aphanomyces spec, and Fusarium oxysporum. The seeds are sewn 3 cm deep at a distance of 3 to 5 cm. The seed boxes are then stored in a greenhouse at 17 to 20 ° C. The number of healthy pea plants is determined after 21 days.

The results are shown in the following overview:

active substance % of healthy plants after 21 days of composting 5 96 10 96 12 94 A (known) 15 Dec В (known) 63 inspection (untreated) β - control (sterilized composting) 98

SUBJECT OF THE INVENTION

Claims (1)

SUBJECT OF THE INVENTION A fungicidal composition comprising a solid or liquid carrier and, as active ingredient, a 2- (N-aryl-, N-acyl) aminopropane acetal of the formula I ## STR3 ## in which the radical is C1 -C4 -alkyl, is hydrogen, halo or C 1 -C 4 alkyl, either independently of each other, C 1 -C 4 alkyl or together form a methylethylene chain containing 2 to 3 methylene groups optionally substituted by a methyl or phenyl group and represents a methyl group, optionally substituted by methoxy, ethoxy, methoxyethoxy, triazole or imidazole, or represents a cyclopropyl group.