HU176081B - Stabilized fungicide compositions containing 2-alkoxy-imino-2-cyano-n-carbamoyl-acetamide derivatives - Google Patents

Abstract

Fungicides consist of 10 pts. of a cpd. of formula (I): RON=C(CN)-CONHCONHR1 (I) (where R is methyl or ethyl; and R1 is H, 1-4C alkyl or allyl), e.g. 2-cyano-N-ethyl-carbamoyl-2-methoxyiminoacetamide, and 1-100 pts. of an acidifying agent (pref. succinic acid, monosodium succinate, fumaric acid, monosodium fumarate, maleic acid, monosodium maleate, zinc chloride, zinc sulphate or zinc nitrate) which in 1% solution in distilled water gives a pH of 2-5.7 and which on titration to pH 7 of a 1% soln. in distilled water gives a free acidity of >=2.5 mmol per g of acidifying agent. (I) are known agricultural fungicides.

Description

USA

Stabilized Fungicidal Compositions Containing 2-Alkoxyimino-2-Cyano-N-Carbanoyl Acetamide Derivatives

The 2-alkoxyimino-2-cyano-N-carbamoylacetamide derivatives are disclosed in U.S. Patent No. 2,312,956. German Federal Publication. These preparations are useful as agricultural fungicides, and in particular against late tomato and potato disease and grape mildew.

It has been found that the 2-alkoxyimino-2-cyano-N-carbamoylacetamide derivatives are stable in dilute suspension sprays only in acidic pH media. Surprisingly, in these fungicides, even if the suspension spray is standing for several hours before spraying, especially when the suspension spray is warm, even a neutral or slightly alkaline aqueous medium will cause significant loss of active ingredient. Cyanoacetamide derivatives are often mixed with other fungicides, and in many industrial fungicide formulations, additives significantly degrade the cyanoacetamide derivatives. Degradation in these formulations is particularly problematic since they generally have a low active ingredient content (about 150 ppm), while most co-fungicides are used at concentrations of 1000 ppm or more. It should be noted that degradability is only seen in solutions. Conventional low powder dry powder formulations are very stable.

The present invention also relates to compositions based on 2-alkoxyimino-2-cyano-N-carbamoylacetamide-α stable in an alkaline-aqueous spray. According to the invention, the active compounds are used together with an acidifying agent.

The 2-alkoxy-nino-2-cyano-N-carboxy-α-ethamide derivatives are protected with an acidifying agent from being degraded by the alkaline-aqueous medium, the additives or other fungicides, e.g. in a suspension spray.

The 2-alkoxyiminoacetamide derivatives correspond to the formula (I). In the formula

R is methyl or ethyl;

R 1 is hydrogen, C 1-4 alkyl or allyl.

Acidifying agents having a pH of 2 to 5.7 in 1% distilled aqueous solution and 1% distilled aqueous solution at pH 7 of at least 2.5 mmol / g may be used in the compositions of the present invention. The weight ratio of substituted iminocyanoacetamide derivatives to acidifier in the composition may be from 1: 0.58 to 1: 2.8.

When the fungicidal compositions containing the alkoxyimino-2-cyano-N-carbamoylacetamide derivatives of formula (I) are used as a suspension spray or solution, the pH of the solution should be kept below 7.3, preferably 6.7. At pH 6.7, less than 10% of the cyanoacetamides decompose at 25-30 ° C in 4 hours. An acidifying agent may be added to the suspension spray liquid or solution to adjust the pH to 7.3, preferably to 6.7, but above 3.

Another method of adjusting the pH of the slurry or solution is to add the acidifying agent to the composition containing the cyanoacetamides. This solution is beneficial to the user and ensures proper use of the product. The acidifying grains must be a compound which has a free acidity of 2% in a 1% (w / v) aqueous solution of distilled water and has a pH of between 2 and 5,7 and a 1% (w / w) solution of sodium bicarbonate titrated to ρΗ-7, 5 mmol / g.

However, the free acidity of the 1% distilled aqueous solution of the acidifying agent at pH 7 need not be greater than 22 mmol / g.

The optimum amount of acidifying agent is varied according to the degree of stability desired and the intended spray mixture. In general, compositions having a weight ratio of cyanoacetamide of formula (I) to acidifying agent of from 1: 0.58 to 1: 2.8 are used.

Preferred compounds of formula (I) are: 2-cyano-2-methoxyimino-N-methylcarbamoylacetamide 2-cyano-2-methoxyimino-N-methylcarbamoylacetamide 2-cyano-2 -ethoxyimino-N-ethylcarbamoylacetamide 2-cyano-2-methoxyimino-N-allylcarbamoylacetamide 2-cyano-2-methoxyimino-N-propylcarbamoylacetamide and 2-cyano -2-methoxyimino-N-carbamoyl-acetamide.

Particularly preferred is 2-cyano-2-methoxyimino-N-ethylcarbamoylacetamide. The compounds of formula (I) are preferably used in the form of dry solid compositions, therefore, dry solid acidifying agents are preferred, but liquid acidifying agents may also be used, particularly when applied to carriers with high adsorption capacity. Suitable acidifying agents are acids (organic or inorganic acids), acid salts of polybasic acids, or salts or other compounds (e.g. acid anhydrides, acid chlorides) which give an acid reaction in water and which have the appropriate free acidity when titrated with sodium bicarbonate.

For example, the following liquid acids may be used as adsorbent carriers: acetic acid, propionic acid, phosphoric acid *, caprylic acid, oleic acid, pelargic acid, lactic acid *, gluconic acid * (* acids generally commercially available as concentrated aqueous solutions).

Examples of solid organic acids are abietic acid, adipic acid, ascorbic acid, azelaic acid, benzoic acid, capric acid, chloroacetic acid, chlorobenzoic acid, citric acid, crotonic acid, fumaric acid, gluconic acid, glycolic acid, iminoacetic acid, isophthalic acid, itaconic acid, malic acid, low acid, myristic acid, naphthoic acid, nitrobenzoic acid, oxalic acid, hydroxynaphthoic acid, palmitic acid, phenylacetic acid, phthalic acid, salicylic acid, sebacic acid, sorbic acid, stearic acid, succinic acid, sulfonic acid, tartaric acid, tertiary acid, tertiary acid

Polymerized acids such as polyacrylic acid or polymethacrylic acid or acidic ion-exchange resins may also be used.

Typical acid salts of polybasic acids include alkali metal salts, alkaline earth metal salts, ammonium salts and substituted ammonium salts such as the corresponding hydrogen adipates, hydrogen azalates, dihydrogen citrates, monohydrogen citrates, hydrogen fumarates, hydrogen, maleate, hydrogen phthalate, hydrogen sebacate, hydrogen succinate, hydrogen tartrate, hydrogen terephthalate, hydrogen sulfate, dihydrogen phosphate.

Among the salts which have an acidic reaction with water and which have a free acidity upon treatment with bicarbonate are the mineral acid salts of zinc, iron and aluminum. Examples of such salts are zinc chloride, zinc nitrate, zinc sulfate, ferrous sulfate and aluminum sulfate.

Anhydrides of the aforementioned acids may also be used as acidifying agents. Maleic and phthalic anhydrides are preferred from an economic point of view. In some cases, mixtures of the listed compounds may also be used. Preferred acidifying agents are solid dibasic and tri-basic organic acids having an equivalent weight of 45 to 102, monobasic organic acids having a molecular weight of 46 to 190, and mineral acid salts of zinc.

The most preferred acidifying agents are succinic acid, fumaric acid, maleic acid, their monosodium salts, and zinc sulfate, chloride and nitrate. As mentioned above, fungicidal compositions containing 2-alkoxyimino-2-cyano-N-carbatnoylacetamide derivatives are often used in low concentration (0.35-1.0 x 10 ^-3 mole) suspension spray or solution. Although natural waters may contain 12 to 14 x 10 ^-3 n residual alkalinity (such as bicarbonate), more than 7 X 10 ³ n carbonates plus bicarbonate are extremely rare in natural waters.

Compared to these levels, each commercially available fungicidal mixture has a relatively small increase in the (residual) alkalinity of the water. However, it is not necessary to neutralize more than half of the bicarbonates in order to obtain the appropriate pH. Thus, usually no more than about 10 molar equivalents of acidifying agent per cyanoacetamide derivative are required. On the other hand, the lower limit for hydrogen carbonate in well water is about 2 x 10 < ^{3 >} n, of which at least 15% must be neutralized. Thus, formulations containing less than 0.3 molar equivalents of acid per mole of cyanoacetamide may be used in a relatively narrow range, i.e., only slightly alkaline water, and the excipients and other known fungicides used, if appropriate, should be carefully selected. .

Therefore, it is preferred to use 0.3 to 10.0 molar equivalents of acidifying agent per mole of cyanoacetamide derivative. More generally, compositions containing from 0.7 to 10.0 molar equivalents of an acidifying agent per mole of cyanoacetamide derivative may be used. In general, compositions containing 1.0 to 5.0 molar equivalents of an acidifying agent per mole of cyanoacetamide derivatives are suitable.

Many acids form salts with the 2-alkoxyimino-2-cyano-N-carbamoylacetamide derivatives. Since such salts give an acidic reaction, the acid contained therein is suitable for neutralizing alkaline water. Thus, the amount of acid to be used is the same, either in the free state or when bound to the fungicidal agent.

When salt formation occurs in a relatively concentrated dry powdered mixture of cyanoacetamide and acid, the process is usually accompanied by lumping, which results in a reduction of the salt dispersibility. In such cases, it is advantageous to form the salt prior to final finishing.

In some cases, the salt may be isolated from the solution containing the acid and the fungicidal active ingredient by precipitation or simply by mixing the two components into a suspension. In a more general procedure, acidic and substituted cyanoacetamide are milled and any salt formation is allowed to occur prior to formulation. Raising the temperature from 40 ° C to 100 ° C accelerates the process so that the final, physically solid powder composition can be obtained in one hour instead of one day.

Extremely low reactivity with insoluble acids, e.g. terephthalic acid, salt formation does not take place at all, or if so, the process is so slow that it has no practical significance. In relatively dilute formulations, with about 10% or less cyanoacetamide, the concentration of the cyanoacetamide is so small that it is not necessary to form the salt in a preliminary step to avoid lumping.

For practical use, the compositions may be prepared in conventional manner. In the case of concentrates or premixes, the composition is predominantly composed of the cyanoacetamide derivative and the acidifying agent, usually containing a surfactant and / or an inert carrier. Further, the compositions may also contain minor amounts of foaming, corrosion, lumping, etc. inhibitory additives may also be added.

The preparation of preparations is described, inter alia, in the following publications:

No. 312,956 German Federal Publication Document;

No. 576,834; Column 5, Column 7, Line 36, Line 70, and U.S. Pat

Nos. 1-14, 17, 106, 123-140. s. examples. 30

No. 560,616; Column 3, Column 7, Line 48, Line 26, and Figures 3 to 9, 11 to 18; s. examples.

Torgenson: Fungicides I. Chapter 6: E. Somers, The Formula (Academic Press, New York, 1967) 35

Because cyanoacetamide derivatives are used in relatively low concentrations, it is often possible to simply mix the ground mixture of the compound and the acidifying agent with a pre-formulated commercial composition of other fungicides to form a ready-to-use mixture. Of course, it is also possible to mix all of the ingredients used together to form the final product.

Fungicides which may be used in combination with cyanoacetamide derivatives are: 45 maneb, zineb and mancozeb; metiram, ziram, ferban and other dimethylthiocarbamate salts; thiram, folpet, captan, captafol, dichlorofluoride, dodine, 2,4-dichloro-6- (6-chloroaniline) -oc-triazine; benomyl, carbendazim, thiabedazole, methylthiophanate, chlorothalonil, chemically bonded copper containing substances such as. copper oxychloride, basic copper sulfate, copper hydroxides, copper oxides and copper oxychloride sulfates.

Combinations of cyanoacetamide derivatives and maneb or mancozeb are particularly useful because they have 55 fungicidal efficacy. However, since maneb is unstable in the presence of acids and cyanoacetamide derivatives in the presence of alkalis, only the zinc sulfate, chloride or nitrate of the acidifying agents can be used in combination with the cyanoacetamide derivatives and maneb 60 listed above.

GBoxysulphate is particularly useful in these formulations. These zinc salts stabilize maneb compositions against the degrading effect of acids and at the same time have 65 acidifying effects to stabilize cyanoacetamide derivatives. U.S. Patent Nos. 3,025,042 and 3,379,610 disclose how to use zinc salts to stabilize a maneb composition. If sufficient zinc salt is present to stabilize the maneb composition, other acidifying agents selected from those listed above may be used to protect cyanoacetamide derivatives from the action of alkaline agents. However, it is important that at least 2 mol% of the zinc ion is present in the formulation with respect to the maneb. Of course, the zinc salt in excess of the amount required to protect the maneb composition is useful as an acidifying agent for the cyanoacetamide derivative. In practice, compositions containing maneb and cyanoacetamide derivatives should contain from 2 to 15 mol%, more preferably from 4 to 10 mol%, of zinc per maneb.

The cyanoacetamide derivative: maneb ratio is not critical, but in addition to the amount of zinc needed to protect the maneb, the total amount of acidifying agent required to stabilize the cyanoacetamide derivatives must be within the limits described above.

The composition and method of preparation of the compositions of the invention are illustrated by the following examples.

Example 1

2-cyano-2-methoxyimino-N-ethylcarbamoylacetamide 50% zinc sulfate, monohydrate 40% sodium dioctylsulfosuccinate 1% sodium alkylnaphthalene sulfonate 1% methyl cellulose (15 eps) 1 s% attapulgit 7 s%

The ingredients are mixed and crushed into a hammer mill to pass through a 0.3 mm mesh sieve.

The stability of the active ingredient formulated as described above is compared to that of an analytically pure active ingredient. The active ingredient is used at a concentration of 300 ppm in the following media:

(a) basic sodium carbonate-softened water (initial pH 10.2, basicity: 0.66x10 ~ ³ n; base weight carbonate), and

b) strongly alkaline with sodium hydrogen carbonate water (pH 8.8; basicity: 13xl0 ~ ^J n).

After four hours at room temperature in these various experimental waters, the following results were observed:

(a) residues of the active substance in water She/ pH (b) water active substance residue 0 / pH pure active ingredient /She 43 7.7 / 0 16 8.2 Example 1 preparation 78 6.9 87 7.2

Other compounds of formula (I) may be used in the above formulation as fungicidal active compounds with similar results.

Example 2

a) 2-Cyano-2-methoxyimino-N-ethylcarbamoyl;

Acetamide 50% by weight succinic acid 49% by weight synthetic fine silicic acid 1% by weight powder is mixed and ground in a hammer mill.

b) Finely grind 2-cyano-2-methoxyimino-N-ethyl · carbamoylacetamide.

Materials a) or b) are mixed with the following commercial fungicides. One part by weight of the active ingredient of composition (a) or (b) is added to the compositions listed below.

ej 16 parts "Parzate" —75% zineb fungicide [active ingredient: ethylene bis (dithiocarbamic acid) zinc salt] (manufactured by Du Pont).

d) 16 parts Thylate - 65% by weight thiram fungicide (active ingredient: tetramethylthiuram disulphide) (manufactured by Du Pont).

(e) 16 parts Phalten - 50% w / w folpet fungicide [active ingredient: N- (trichloromethylmercapto) phthalimide] (manufactured by Chevron).

f) 8 parts "Benlate" - 50 wt% benomyl fungicide (active ingredient: [1- (Butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester] (manufactured by Du Pont).

(g) 12 parts 'Kocidc' containing 101 to 83% by weight of copper hydroxide fungicide (manufactured by Kennecot).

(h) 64 parts "Viricuivre" - 50% w / w Rc-oxychloride fungicide (manufactured by Pepro).

i) 16 parts Captan-50% chaphan fungicide (active ingredient: N-trichloromethylthio-3a, 4,7,7a-tetrahydro-

phthalimide) (manufactured by Stauffer).

(j) 24 parts 'Bravo' - 75% chlorothalonil fungicide (manufactured by Diamond Shamrock).

k) 16 parts "Polyram" - 80% by weight complex dithiocarbamate fungicide (manufactured by Niagara).

The mixture is then in either case of distilled water in another case, a solution of 4.7 × 10 ^_3 N sodium hydrogen carbonate, in proportions such that the mixture is approx. Contains substituted acetamide at a concentration of 150 ppm. After 4 hours, the suspensions were inspected and the remaining amount of substituted acetamide determined. The pH is also recorded over a period of 1-4 hours. The results are summarized in the table below.

distilled water 4.7 X 10 -'n Bicarbonate ♦% of active ingredient PH residue of active ingredient *% pH Parzate ac 100 4.6-4.7 93 6.7-6.9 blends into 82 7.5-7.6 41 8.2-8.1 Thylate ad 96 4.0-4.1 92 6.7-6.8 mixtures bd 95 7.0 49 8.4 to 8.2 Phaltan ae 100 4.2-4.4 97 6.7-6.8 blends into 94 7.4-7.1 50 8.2 to 7.8 Benlate af 100 4.0 100 6.7 mixtures bf 100 6.9 55 8,4-8.2 Kocide ag 100 6.1 92 6.9 mixtures bg 77 7.9-7.8 38 8.5-8.3 "Viricuivre" ah 100 5.6-5.7 100 6.6-6.8 mixtures bh 99 7.2-7.1 8.1-8.0 Captan et al 100 5.9-6.0 100 7.07.2 mixtures bi 47 8.3 to 8.0 48 8.2 to 7.9 "Bravo" aj 100 4,2-4.5 100 6.7-6.8 mixtures bj 84 7.7 34 8.4 to 8.2 Polyram Ac 100 4.5-4.6 97 6.8 mixtures bk 87 7.5 49 8.2-8.0

*% of initial 2-cyano-2-methoxyimino-N-ethylcarbamoylacetamide. ♦ * was not tested after the four hour experiment.

It will be appreciated that the acidifying agent stabilized the 2-cyano-2-methoxyimino-N-ethylcarbamoylacetamide in the mixtures, particularly in alkaline water. There was no case where a decrease in suspension stability was observed in the mixture.

Example 3

2-Cyano-2-methoxyimino-N-methylcarbamoylacetamide 10% by weight fumaric acid 10% by weight zinc sulfate 2.5% by weight commercially prepared 80% maneb 77.5% by weight [active ingredient: ethylcis-bis] - (dithiocarbamic acid) magnesium salt] (Manzate, manufactured by Du Pont)

The mixtures are mixed and ground in a hammer mill. The powder was added to 0.15% water containing 4.7 X 10 ^-3 N sodium bicarbonate and allowed to stand for 4 hours. At the end of the experiment, well over 90% of the substituted acetamide is retained and the pH is stable around pH 6.7. A similar formulation, without acidifying agents (fumaric acid, zinc sulphate), produces a pH range of 8.4 to 7.9 and after 4 hours only about 80% of the initially substituted acetamide.

23% remain.

Example 4

2-cyano-2-methoxyimino-N-propylcarbamoylacetamide 30% terephthalic acid 60% synthetic fine silica 8% sodium alkylnaphthalene sulfonate 0.5% methyl cellulose (15 cps) 1, 5s%

The ingredients are mixed and ground in a hammer mill to obtain a powder through a 0.3 mm mesh sieve. This formulation, when kept in natural alkaline water, exhibits better stability than conventional formulations without acidifying agent. In the above example, terephthalic acid can be replaced with the same solid acidifying agents as listed above.

As mentioned above, for some acids, shelf life may be limited by salt formation or products may clump in storage. If desired, the product should be stored overnight at 50 ° C to 80 ° C and ground again.

Example 5

The biological efficacy of the acidified formulation of Example 1 is compared to a non-acidifying formulation. Composition without acidifying agent: 2-cyano-2-methoxyimino-N-ethylcarbamoylacetamide 80% sodium dioctylsulfosuccinate 1sec / _o sodium lignin sulfonate 2% kaolinite 17sec %

Ten parts by weight of the above salt are mixed with the following components:

fumaric acid 2.8 parts by weight sodium dioctylsulfosuccinate 1.0 parts by weight commercially available mancozeb (Manzate ^R 200) 80.0 parts by weight (active ingredient: magnesium zinc ethylene bis-dithiocarbamate) attapulgit 6.2 parts by weight

The components are mixed and passed through a hammer mill to obtain a powder through a 0.3 mm mesh screen. The product remains stable for a prolonged period of time when suspended at a concentration of 1500 ppm in alkaline water with a residual alkalinity of 5.5 x 10 10 and has good fungicidal activity.

Example 7

A thick slurry of 383 parts of a technical grade 2-cyano-2-methoxyimino-N-ethylcarbamoylacetamide and 117 parts of commercially available fumaric acid in 1200 parts of water for 20 minutes was filtered and dried. This salt may be combined with other components described below to provide physically stable wettable powder formulations.

salt as described above 25.8% by weight fumaric acid 50.2% by weight sodium dioctylsulfosuccinate 1.0% by weight sodium lignin sulfonate 3.0% by weight attapulgite 20.0% by weight

The components are mixed and ground in a hammer mill. Spray mixes containing 80 ppm of active ingredient are prepared in distilled water and left in water of Example 1 (a) for 5 hours before being sprayed on tomato plants. The plants are allowed to stand overnight and inoculated with the spores of late tomato pest. The test results are as follows:

Effect against Late Tomato Disease%

Preparation distilled water (a) Water treated with acidifying agent 100 99 Untreated 100 0

Example 6

A mixture of 383 parts of technical grade 2-cyano-2-methoxyimino-N-ethylcarbamoylacetamide and 2055 parts of methanol is heated to dissolution and 117 parts of commercially available fumaric acid are added with continuous heating. When dissolution is complete, the solution is cooled, the precipitate is filtered off and dried. 428 parts by weight of salt are obtained, containing 2 moles of cyanoacetamide per mole of fumaric acid. Methanol can be recycled several times and the following operations yield 490-495 parts by weight of salt.

The mixture is mixed and ground in a hammer mill. The composition is well dispersible both before and after prolonged storage and can be chemically stable in natural alkaline water.

Example 8

2-Cyano-2-methoxyimino-N-ethylcarbamoylacetamide 20% by weight fumaric acid 56% by weight sodium dioctylsulfosuccinate 1% by weight sodium lignin sulfonate 3% by weight attapulgite 20% by weight

The components are passed through a hammer mill to obtain a powder through a 0.3 mm mesh screen. The powder was kept overnight at 85 ° C and then again wiped in a hammer mill. A physically stable formulation with good properties is obtained.

Example 9 Commercial Copper Oxychloride (50% Copper, Pepro "Viricuivre") 96.29%

2-cyano-2-methoxyimino-N-ethylcarbamoyl

-acetamide 2.25% by weight fumaric acid 1.46% by weight

The components are mixed and passed through a hammer mill to obtain a wettable powder which has good fungicidal activity in alkaline water. Acidification does not cause phytotoxic symptoms.

Example 10

2-Cyano-2-methoxyimino-N-allylcarbamoylacetamide 20% by weight fumaric acid 56% by weight sodium dioctylsulfosuccinate 1% by weight sodium lignin sulfonate 3% by weight attapulgite 20% by weight

The components are passed through a hammer mill to obtain a powder through a 0.3 mm mesh screen. The powder was kept at 85 ° C overnight and then ground again in a hammer mill.

An improved stability formulation is obtained in an alkaline-aqueous medium.

Claims (10)

Claims 1. A stabilized fungicidal composition containing a cyanoacetamide derivative as an active ingredient, optionally in the presence of another known non-degradable fungicide (ck), preferably in the form of a permeate, characterized in that it is present in an amount of 1.5-50% by weight. The fungicidal active ingredient of formula (1) - in the formula (I): R is methyl or alkyl and R 1 is hydrogen, C 1 -C 4 acyl or allyl, and 1.40 to 60% by weight of an acidic acid containing from 0.58 to 2.8% by weight of the active ingredient of the formula (1) in a distilled aqueous solution of pH 2 to 5.7 and a free acidity of at least 2.5 millimoles / g in a 1 weight strength aqueous solution of titrate ρΗ-7-rc with sodium bicarbonate; 0.1 to 97.1% by weight with conventional excipients - preferably carriers, diluents, wetting agents and adjuvants; and if the composition contains a known magnesium salt of ethylene bis (dithiocarbamic acid) as a fungicide, at least a portion of the acidifying agent is a zinc salt. 2. The composition of claim I, wherein the fungicide of formula I is Z-cyano-Z-methoxyimino-N-ethylcarbamoylacetamide, 2-cyano-2-methoxyimino-N-methylcarbamoyl-acetamide, 2-cyano-2-ethoxyimino-N-ethyl carbamoyl-acetamide, 2-cyano-2-methoxy-immobilized N-carbamoyl-Alfil acctamidot, Or 2-cyano-2-methoxyimino-N-propylcarbamoylacetamide; 2-cyano-2-methoxy-imino-N-carbamoyl-acetamide 5 included. (Priority: January 30, 1975) 3. The composition of claim 1 wherein the fungicide of formula I is 2-cyano-2-methoxyimino-N-ethylcarbamoylacetamide. (Priority: January 30, 1975) 10 An embodiment of the composition of claim 1, wherein the acidifying agent comprises an organic acid of two to three bases having an equivalent weight of 45 to 102, a monobasic organic acid having an equivalent weight of 46 to 190 or a zinc salt formed with a mineral acid. (Priority: January 30, 1975) An embodiment of the composition of claim 1, wherein the acidifying agent is succinic acid, succinic acid monosodium salt, fumaric acid, fumaric acid monosodium salt, maleic acid, maleic acid moiety. It contains 20 non-sodium salts, zinc chloride, zinc sulfate or zinc nitrate. (Priority: January 30, 1975) An embodiment of the composition of claim 1 in the form of a spray, characterized in that the fungicidal compound of formula (I) wherein R 25 and Rj are as defined in claim 1 and contain, in addition to the excipients, sufficient acidifying agent to adjust the pH to between 3 and 7.3. (Priority: January 30, 1975) The embodiment of the spray according to claim 6, It is characterized in that it contains the necessary amount of acidifying agent to adjust the pH to between 3 and 6.7. (Priority: January 30, 1975) 8. Figures 1-7. An embodiment of the composition according to claims 1 to 4, characterized in that it is of formula (I) 35 fungicidal active ingredients, wherein R and R 1 are as defined in claim 1, and at least 2 mol% of the magnesium salt of ethylene bis (dithiocarbamic acid) and the magnesium salt of ethylene bis-dithiocarbamic acid, known as the fungicide. zinc 40 chloride, zinc sulfate or zinc nitrate. (Priority: January 30, 1975) 9. The composition of claim 8, wherein R is methyl and R 1 is is an ethyl group of formula (I) Contains 45 fungicides and zinc sulfate. (Priority: January 30, 1975) 10. A composition according to claim 8 embodiment, wherein R = methyl and fun- formula _(wherein A is an ethyl group (I), R It contains 50 gicidal active ingredients and, as an acidifying agent, a bi-basic or tri-basic organic acid having an equivalent weight of 45 to 102, a monobasic organic acid having an equivalent weight of 46 to 190 or a zinc salt with a mineral acid. (Priority: December 12, 1975 wage 12)