NO141971B - FUNGICIDE PREPARATIONS FOR THE CONTROL OF PLANT DISEASES IN PLANTS - Google Patents

Description

The present invention relates to fungicidal preparations for the control of fungal diseases in plants, and the peculiarity of the preparations according to the invention is that they contain a compound with the general formula

in which

R is an optional monohalogenous linear or branched alkyl radical containing from 1 to 18 carbon atoms, an alkenyl, alkynyl or alkoxyalkyl radical, the hydrocarbon part of these three types of radicals containing from 2 to 5 carbon atoms, a cyclohexyl radical, a phenyl radical, a phenyl ( C ^ - C3) alkyl radical, or a tetrahydrofurfuryl radical,

M stands for an ammonium cation, ammonium substituted by 1 more

4 alkyl or hydroxyalkyl radicals containing from 1 to 5 carbon atoms or a phenyl radical, or a cation of a

metal from the group consisting of alkali metals, alkaline earth metals, zinc, manganese, copper (I) and (II), iron, nickel and aluminium, and

n is an integer corresponding to the valence of M.

These and other features of the invention appear in the patent claims.

Some of these compounds are known in and of themselves. V.V. Orlovski et al., Journal of Gen. Chem. USSR, vol. 42, p. 1924

(1972) describes the preparation of numerous salts of mono-alkyl phosphites and especially monoethyl phosphites with metal-

or ammonium cations substituted to a greater or lesser extent, but the fact that these compounds have fungicidal properties is not mentioned.

It has now been found that these compounds have excellent fungicidal properties, especially with regard to various types of molds, such as e.g. wine powdery mildew, tobacco powdery mildew and hop powdery mildew, and is therefore suitable for use as an ingredient in fungicidal preparations.

These compounds can be prepared using the following general methods (cf. Houben-Weyl, volume XII/2).

First of all, phosphonates can be produced by transesterification of a dialkylphosphonate with phosphoric acid (E.E. Nifantev, L.P. Levitan, CA. 1107e 1966) in accordance with the following reaction scheme:

O-ethylphosphonate was prepared by the following procedure:

an equimolecular mixture of 0,0-diethyl phosph onate and phosphoric acid is heated for 6 hours at 150°C. A liquid with a refractive index n = 1.4211 and a density d = 1.0043 (20°C) is obtained in quantitative yield.

The following compounds can also be prepared using this method: O-methylphosphonate, O-n-hexylphosphonate, O-isooctylphosphonate, O-n-nonylphosphonate, O-n-decylphosphonate, O-n-dodecylphosphonate, O-n-hexadecylphosphonate, O-cyclohexylphosphonate, O-phenylphosphonate, O- benzyl phosphonate.

It is also possible to obtain esters of this type (cf. Houben-Weyl, volume XII/2, page 6) by hydrolysis of a phosphoric acid dichloride with 2 equivalents of water in accordance with the following reaction principle:

In particular, O-octylphosphonate can be produced by this method.

As regards salts, these can be produced by at least two methods:

the first method comprises (cf. Houben-Weyl, volume XII, page 7) hydrolysis or saponification of an 0,0-dialkylphosphonate in accordance with the following scheme:

This method is particularly suitable for alkali metal salts and ammonium salts.

I - Alkali metal and ammonium salts.

Saponification is carried out using an inorganic or organic base in an aqueous solution. The reaction takes place within 1 to 4 hours at a temperature of from the ambient temperature to the backflow temperature (aqueous medium). The products obtained, which are liquids or solids, generally soluble in water, are isolated by removing any water and solvent.

Sodium O-ethylphosphonate He prepared in this way. An equivalent of soda in aqueous alcohol solution is added dropwise with stirring to an aqueous alcoholic solution of 0,O-diethylphosphonate. After standing for 2 hours, alcohol and water are removed by distillation under reduced pressure in a water bath. The solid residue is recrystallized from absolute alcohol.

Melting point: > 300°C, yield 68%.

Analysis for C^HgC^NaP

The following salts were prepared using this method:

The ammonium salts are obtained in the following manner, which is illustrated in connection with the production of ammonium O-ethylphosphonate: 0.036 mol of 0,O-diethylphosphonate is dissolved in a 25% aqueous ammonia solution. After standing for 1 hour, the solution is evaporated under reduced pressure in a water bath. The initially rubbery and colorless residue crystallizes. Crystals in the form of colorless needles are obtained by crystallization in a mixture of ethanol and acetone.

Yield: 87%. m.p. 99 - 100°C.

Analysis for C2H10NO3P

Other alkali metal salts, whose properties and where necessary, the special preparation conditions are shown in the following table, were obtained by changing the saponification base and/or the alkyl radical in the method described above:

II - Substituted ammonium salts

a) Alkanolamine and alkylamine salts

Production of monoethanolammonium O-ethylphosphonate.

0.05 mol of 0,O-diethylphosphite is poured into an aqueous solution of one equivalent of monoethanolamine. The reaction is carried out for 1 hour at 50°C. Removal of water by evaporation leaves a water-soluble oil.

Dividend: 35% n£<u> 1.4595.

Analysis for C4H14N04P

Similar compounds, whose properties are shown in the following table, were prepared by the same process. The yields are more than 85% in each case. Another method for producing alkylammonium salts involves reacting an ammonium halide with a dialkyl phosphite in accordance with the following reaction principle:

(cf. Orlowskii et al, J. Organ. Chem, USSR, 1972, vol. 42, pp. 1924 to 1927).

The following compounds were prepared using this method:

—monoethylammonium O-ethylphosphonate

-diethylammonium O-ethyl phosphate

-triethylammonium O-ethylphosphonate.

b) Quaternary ammonium salts

Preparation of tetramethyl ammonium O-methylphosphonate

0.05 mol of 0,O-dimethylphosphite is added to an equivalent amount of trimethylamine in solution in acetone. The reaction mixture is kept at 50 to 60°C for 2 hours.

The evaporation of acetone leaves behind a highly hygroscopic water-soluble solid.

Yield: 77%

Analysis for C5HlgN03P

The corresponding 0-ethyl and 0-isopropyl derivatives were obtained by the same method, 0,0-dimethylphosphite being replaced by O-methyl-O-ethyl respectively. O-methyl-O-isopropylphosphonate. The reaction was carried out at 70 to 100°C in acetonitrile. The solids obtained were recrystallized from acetone.

Tetramethylammonium O-ethylphosphonate

Yield: 94% m.p. 134°C.

Analysis for CgH^NOgP

Tetramethylammonium O-isopropylphosphonate

Yield: 92% m.p. 153°C.

Analysis for CyH^NC^P

III - Toverdiqe metal salts

A metal halide reacts with a dialkyl phosphite according to the following reaction nucleus:

(cf. Orlovskii et al, J. Organ. Chem. USSR, vol. 42, pages 1924-1972).

Calcium O-ethylphosphonate was prepared in this way.

A mixture of 11 g (0.01 mol) calcium chloride with 2.8 g (0.02 mol) 0,O-diethylphosphonate is heated with stirring for 2 hours to 110 to 130°C. The mixture is cooled and a precipitate is obtained which, after filtration and washing, gives white crystals which melt above 420°C and with a yield of 96%.

Analysis for C4H120gP2Ca

The following salts can be obtained in a similar way by replacing the starting salt with respectively:

-barium O-ethylphosphonate

-zinc O-ethylphosphonate

Magnesium O-ethylphosphonate

0.2 mol of 0,O-diethyl phosphite is added to a suspension of 0.1 mol of magnesium oxide in 100 cc of distilled water. The exothermic reaction is carried out with stirring for 2 hours at 50°C. After filtration, the water is evaporated from the filtrate leaving a white solid which is washed with acetone and then dried.

Yield: 100% m.p.: 300°C

Analysis for C^H^M<g>O<g>P,,

The following table shows the properties (appearance, melting point, solubility in water) and analysis of other metal alkyl phosphonates obtained in the same way as in the previous example. Unless otherwise stated, yields are more than 70% and most are quantitative. In the case of manganese salts, the metal oxide is replaced by a carbonate.

IV - Salts obtained by a double exchange reaction.

a) Synthesis via the barium salt

Zinc O-n-butylphosphonate.

0.05 mol of O-n-butylphosphonate and 0.05 mol of barium oxide are dissolved in 150 cc of distilled water. Barium O-n-butylphosphonate is precipitated.

A solution of 0.05 mol zinc sulphate heptahydrate in 200 cc of distilled water is then added and this causes barium sulphate to precipitate. It is separated by filtration or centrifugation. The clear filtrate is evaporated to dryness and gives a highly viscous liquid which is dried in vacuum. The liquid is soluble in water.

Yield: 82%

Analysis for CoH„_<0>,<PoZ>n

8 20 6 2

The products whose properties are indicated in the following table were obtained by changing either the alkyl radical or the metal in the process described above. Unless otherwise stated, dividends are more than 70%.

b) From the sodium salt

Aluminum O-isopropylphosphonate

Sodium O-isopropylphosphonate is prepared. A solution of 0.06 mol of aluminum nitrate with 9 molecules of water in 30 cc of distilled water is added to a solution of 0.18 mol of the aforementioned compound in 150 cc of distilled water. Aluminum 0-n-propylphosphonate is precipitated. The precipitate is centrifuged, washed with water and then with acetone and finally dried in vacuum to give a white solid which is

insoluble in water.

Yield: 60%. Temp. : >300°C.

Analysis for CgH^AlOgP^

The following compounds were prepared by the same method from analogous sodium O-alkylphosphonate derivatives. The iron (III) salts were obtained by replacing the aluminum nitrate with ferric iron nitrate.

The properties of all these compounds are indicated in the following table. Unless otherwise stated, dividends are more than 70%.

V- Iron salts

Iron O-ethylphosphonate

This compound is prepared by the method (Chem. Ber. 90, p.811), comprising the reaction of ferric chloride with three equivalents of ethyl phosphoric acid. A solid which melts above 300°C is obtained after filtration and washing.

Iron O-(2-chloroethyl)-phosphonate

This compound is prepared by ORLOVSKI<*>'s method described earlier, by replacing soda with ferric chloride. It is possible to obtain the iron salts of the phosphonates, e.g. iron O-(2-chloroethyl)-phosphonate which decomposes at about 135°C.

Analysis for C.-H.. CC1„FeOnP„

1 6 1 b 3 9 3

The following examples illustrate the fungicidal properties of the following compounds:

1 - ammonium 0-methylphosphonate

2 - ammonium O-ethylphosphonate

3 - sodium O-ethylphosphonate

4 - calcium O-ethylphosphonate

5 - ammonium O-n-propylphosphonate 6 - ammonium O-isopropylphosphonate

7 - ammonium O-n-butylphosphonate

8 - ammonium O-n-hexylphosphonate 9 - ammonium 0- £{ 2-ethyl)-n-hexyl/phosphonate 10- sodium 0-n-octylphosphonate 11- sodium O-n-dodecylphosphonate 12- sodium O-n-hexadecylphosphonate 13- ammonium 0-allylphosphonate 14 - ammonium O-methoxy ethylphosphonate 15- ammonium O-cyclohexylphosphonate 16- ammonium O-benzylphosphonate 17- ammonium O-tetrahydrofurfurylphosphonate 18- sodium 0-methylphosphonate 19- tetramethyl ammonium 0-methylphosphonate 20- dicyclohexyl ammonium 0-methylphosphonate 21- potassium O-ethylphosphonate 22- magnesium O-ethylphosphonate 23- barium O-ethylphosphonate 24- zinc O-ethylphosphonate

25- manganese O-ethylphosphonate 26- aluminum O-ethylphosphonate 27- ironClII) O-ethylphosphonate 28- copper(lI) O-ethylphosphonate 29- nickel(II) O-ethylphosphonate 30- magnesium O-n-propylphosphonate 31- sodium O-isopropylphosphonate 32 - kaMum O-isopropylphosphonate 33- aluminum O-isopropylphosphonate 34- sodium O-n-butylphosphonate 35- calcium O-n-butylphosphonate 36- ammonium O-sec.-butylphosphonate 37- aluminum O-sec. -butyl phosphate 38- calcium 0-n-ZT2-ethyl)n-hexyl/phosphonate 39- sodium O-methoxyethylphosphonate 40- magnesium O-methoxyethylphosphonate 41- ammonium O-propargylphosphonate 42- ammonium O-phenylphosphonate

EXAMPLE 1: Experiment in vivo with Plasmopara viticola in vine plants.

a)_ £££YÉ!2iiY_5^!}^nÉi.iD2

The leaves of potted vine plants (Gamay type) are sprayed on

the underside using an atomizing syringe with an aqueous suspension of a wettable powder with the following composition (percentage by weight):

in the necessary dilution containing the active material to be examined in the relevant dose. Each experiment was repeated three times.

After 48 hours, the plants were contaminated by spraying the leaves

on the underside with an aqueous suspension of approximately 80,000 units/cc of spores of the above-mentioned fungus.

The pots are then placed in an incubation cell at 20°C/100% relative humidity for a period of 48 hours.

The plants were examined 9 days after infection.

Under these conditions, it was found that at a dose of 0.5 g/l, compounds 1 - 9, 11 - 22, 24, 26 - 30, 32 - 38 and 40 - 42 provided complete protection, while compounds 23, 25, 31 and 39 provided good protection.

In addition, it was found that none of the investigated compounds showed the slightest phytotoxicity.

b) Treatment after infection.

The procedure is as described in a) above, with the exception of i

that the plants are first infected and then treated with the active material to be examined, as the plants are examined 9 days after infection.

Under these conditions, it was found that in a dose of 1 g/l

stopped connections 1 - 8, 10 -'29, 31, 32, 36 and 40-42-

complete the development of powdery mildew on grapevines.

c) Systemic experiments with root absorption.

A number of vine plants (Gamay type) each adapted in one

pot containing vermiculite and a nutrient solution is sprayed with 40 cc of a solution containing 0.5 g/l of the material to be examined. After two days, the vines are infected with an aqueous suspension containing 100,000 spores/cc of plasmopara viticola. The spores are then allowed to incubate for 48 hours in a room at 20°C/100% relative humidity. The degree of infection is judged after 9 days in relation to an infected control sample which had been sprayed with 40 cc of distilled water.

Under these conditions, it was found that in this dose of 0.5 g/l

compounds 1 - 18, .20 - 35 and 37 42, absorbed through the roots, gave total protection to the vine leaves against powdery mildew, and this clearly shows the systemic nature of these compounds.

EXAMPLE 2: Open-air experiment with wine-melduqq:

Groups of 5 vine plants (Gamay type) are sprayed every 8 days from

5 July to 20 August with an aqueous solution containing 200 g/hl of active material, or in one case, a wettable powder with the following composition (weight basis):

Mildew (plasmopara viticola) appeared from 24 July onwards. Natural infection was considerable. In August, the vine plants are sprayed in such a way that the leaves are kept constantly moist. The attacks by fungi were considerable and in September the growth of powdery mildew was promoted by particularly damp weather.

At the end of October, the number of mildew-infested areas per unit area counted on the leaves that had been effectively treated.

Under these conditions, it was found that the control samples showed 160 powdery mildew-infected areas per surface unit, while the surface units treated with compounds 2,3, 4, 21, 22 26, 31 and 39 did not show the slightest sign of powdery mildew.

In addition, the shoots that were not present during the treatments showed only a few powdery mildew-infected areas per surface unit, which fully confirmed the systemic nature of these compounds.

EXAMPLE 3: Test on tobacco plants.

Groups of 5 tobacco plants (PB 91) are treated on 15 June with a wettable powder containing 160 g/l manebe (80%), 300 g/l sodium O-ethylphosphonate and 300 g/l magnesium O-ethylphosphonate (50%). One group is left untreated as a control.

After 48 hours, the plants were artificially infected (with peronospora tabacina) and then showered with finely atomized water. The treatment was then continued only once per week.

An investigation is carried out on 12 August by counting the number of areas infected with powdery mildew per group. The results are shown in the following table:

Other experiments show that the two compounds are also effective against this fungus in curative treatment, and have a systemic effect.

EXAMPLE 4: Avocado trial

Young avocado plants (Persea indica type) are planted in soil infected with Phytophtora cinnamomi, after which the soil is sprayed with a solution containing 3 g/1 aluminum O-ethylphosphonate. Certain plants are left untreated as a control. Under these conditions, it was found after 20 days that the roots of the control plants were completely destroyed, while 90% of the roots of the treated plants were healthy.

EXAMPLE 5; Pineapple experiment

Young pineapple plants are infected with Phytophtora parasitica and then treated 48 hours later by spraying with a solution containing 0.5 g/l calcium O-ethylphosphonate. It was found after 30 days that the fungus was completely inhibited in the treated plants, while the control plants were infected.

EXAMPLE 6: Strawberry plant experiment

10 strawberry plants (type Surprise des Halles) are treated by soaking for 1 hour in an aqueous solution containing 0.2%

calcium O-isopropylphosphonate, is dried and then planted out on 14 June in soil that has been artificially infected with Phytophtora cactorum.

Immediately thereafter and then once every 8 days until then

On 18 July, the plants were sprayed with the same solution, which corresponds to a total supply of 0.5 g of active material per plant.

Plants'-.treated by soaking and spraying with. water became

used as control plants. Under these conditions, it was found on 24 July that the protection given to the strawberry plants was complete, while 76% of the control plants were dead.

EXAMPLE 7: All-purpose plants

10 all-purpose plants (type Yolo wonder) that had already been planted out are transferred on 27 June to pots of soil that was artificially contaminated with Phytophtora capsici. The plants are sprayed immediately and then once every 8 days until 18 July with an aqueous solution containing zinc O-ethylphosphonate so that a total of 0.5 g of active material per plant.

Plants sprayed with water are used as controls.

Under these conditions, it was found that the ten plants were i

retain at the end of August, while the control plants were all dead on 25 July.- All these examples clearly show the remarkable fungicidal effect of these compounds, on the one hand a systemic anti-mildew effect which both prevents and stops the development of wine- powdery mildew, and on the other hand the effect as well

on certain phytophthora.

The compounds have also been found to be extremely effective in controlling other types of parasitic fungi such as e.g. guignardia bidwellii in vine plants, Pseudoperonospora humuli, Bremia lactucae, Phytophtora infestans, Peronospora sp., Phytophtora palmivora, Phytophtora phaseoli, Phytophtora megasperma, Phytophtora

drechsteri and other Phytophtora sp. in plants for temperate climates or tropical climates such as tobacco plants, plant cultures such as onions, peppers, tomatoes, beans, ornamental plants, soybeans, citrus plants, cocoa plants, coconut palms, rubber plants.

The compounds are therefore particularly suitable for use in the preventive or curative treatment of fungal diseases in plants, especially fungal diseases caused by phycomycetes and ascomycetes in the aforementioned vegetable varieties, but also more generally in agriculture, horticulture, flower gardens, ordinary gardens, and more particularly in a greenhouse.

The compounds can be used with advantage in a mixture with each other or with other known fungicides, such as e.g. metal dithiocarbamates (maneber, zinebe, mancozebe), basic salts or hydroxides of copper, (oxychloride, oxysulphate), (tetrahydro)phthalimides (captane, captafol, folpel), N-(l-butyl carbamoyl)-2-benzimidazole, methyl -carbamate (benomyl), 1,2-di-(3-methoxy or ethoxy)-carbonyl-2-thioureido benzenes (thiophenates), methyl 2-benzimidazole carbamate, etc, either to complete the range of action of these compounds or to increase their long-term impact.

It has also been found that the phosphonate compounds can be mixed with other fungicidal, anti-mildew phosphorus derivatives, especially 2-hydroxy-1,3,2-dioxaphospholanes, p-hydroxyethyl phosphites and phosphoric acid and its salts.

The doses in which the compounds are used can vary within wide limits, both depending on the virulence of the fungal species and the climatic conditions. Doses of from 0.01 to 5 g/l active material are usually suitable.

For their practical application, the compounds are rarely used alone. They most often form parts of mixtures which usually contain a carrier and/or a surface-active agent in addition to the active compound.

As a carrier, an organic or inorganic, natural or synthetic material is most often used in connection with the active material to facilitate its application. the plant, before or to the soil, or its transport or treatment. The carrier can be solid (clays, natural or synthetic silicates, resins, waxes, solid iodizing agents) or liquid (water, alcohols, ketones, petroleum fractions, chlorinated hydrocarbons, liquid

made gases).

The surface-active agent can be an ionic or non-ionic emulsifier, dispersant or wetting agent such as e.g. salts of polyacrylic acids and ligninsulfonic acids, condensates of ethylene oxide with fatty alcohols, fatty acids or fatty amines.

The mixtures can be produced in the form of wettable powders, soluble powders, loose powders, granules, solutions, emulsifiable concentrates, emulsions, slurried concentrates and aerosols.

The wettable powders can be prepared in such a way that they contain from 20 to 95 percent by weight of the active material, and they normally contain, in addition to a solid carrier, from 0 to 5 percent by weight of a wetting agent, from 3 to 10 percent by weight of a dispersing agent and if necessary from 0 to 10 percent by weight of one or more stabilizers; agents and/or other additives, such as e.g. penetrants, adhesives or anti-caking agents, dyes, etc.

An example of the composition of a wettable powder is given in

the following.

Water-soluble powders are obtained by mixing from 20 to 95% by weight of the active material, from 0 to 10% of an anti-caking agent, the rest being a water-soluble filler, most often a salt.

An example of a composition of a soluble powder is given:

Aqueous dispersions and emulsions, - e.g. mixtures obtained

by diluting a wettable powder or an emulsifiable concentrate

funnel with water can be used and these emulsions can then be of the water-in-oil type or of the oil-in-water type, and can have a thick consistency similar to "mayonnaise".

The mixtures may contain other components, e.g. protective colloids, adhesives or thickeners, thixotropic agents, stabilizers or complexing agents,

as well as other active materials known to have pesticidal properties, especially acaricides or insecticides.

A - The relationship with what is known from French patent literature

No. 1. 529. 738.

This patent document teaches fungicidal preparations containing aminoalkyl phosphites which are effective in treating vine powdery mildew. It is noted that: these compounds have a structure which is not clearly known due to the fact that only the certain empirical form is given, but several interpretations of the formula are given.

no systemic effect is taught, whereas, on the other hand, the essential thing about the present invention is precisely the systemic effect. Known agents against powdery mildew are only effective in preventive treatments and require systematic treatments up to 12 - 14 times during the growth period in order to

achieve phytotoxicity. In contrast, the new fungicides according to the invention work in that they work systemically when they enter the leaves and spread into the plant.

They therefore do not need to be applied as often.

Comparison tests have been carried out with several compounds corresponding to the invention, compared with the compound illustrated in example I in the French patent document with empirical formula C7HgN03P (compound A) under the same conditions as tests according to example I in the present application.

a - Preventive treatment.

The compound A was in an amount of 0.5 g/l in an 80% protection while most compounds according to the present application give a 100% protection. In a quantity ratio of 0.25 g/l, the protection of compound A is 75 Ss in relation to more than 85% for compounds according to the present application.

b - Experiments with systemic effects by absorption by roots.

Under the same conditions as in example Ib gives the compound

A in a ratio of 0.5 g/l a 68% protection while the protection is complete (100%) when compounds according to the present invention are added.

This difference with regard to systemic behavior in greenhouses was found again in experiments in the open field. Under conditions similar to Example 2, compound A did not provide any protection at the end of October and no longer protected the shoots that were not present at the last treatment.

B - Comparison with compounds according to Norwegian patent application no. 74. 4253.

The previous application relates to fungicidal preparations with a systemic effect, especially against wine powdery mildew, and which contain phosphoric acid or salts thereof as an active ingredient. In order to demonstrate the progress of the present invention, comparative experiments were carried out where the difference was judged on the basis of homologues of the two families of compounds.

Under these conditions, phosphoric acid^monoesters and their salts are less phytotoxic in vineyards than phosphoric acid and its corresponding salts.

For example, under the conditions in example 1 concerning systemic action in roots, the compound I (phosphoric acid) caused

and 2 (acidic sodium phosphite) according to the previous application a significant phytotoxicity (severe leaf fall), i.e. of from 30 - 70% in relation to a blank test where monoethyl phosphite and sodium monoethyl phosphite did not show any phytotoxicity.

Likewise, acidic ammonium phosphite (compound 6 according to the previous application) shows a 10-30% phytotoxicity, while ammonium ethyl phosphite, on the other hand, shows no phytotoxicity.

From a practical point of view, this difference between these two families of connections is important as the first is useful with a significantly smaller margin of safety.

Alongside the advantages of the safe and effective systemic effect, the compounds in the fungicidal preparations according to the present invention can be effective in curing plants of powdery mildew attack even if a preventive treatment was not carried out before the attack.

Claims (3)

.1. Fungicidal preparations for the control of fungal diseases in plants, characterized in that they contain a compound with the general formula in which R is an optional monohalogenous linear or branched alkyl radical containing from 1 to 18 carbon atoms, an alkenyl, alkynyl or alkoxyalkyl radical, the hydrocarbon part of these three types of radicals containing from 2 to 5 carbon atoms, a cyclohexyl radical, a phenyl radical, a phenyl (0 ^ - C^) alkyl radical, or a tetrahydrofurfuryl radical, M stands for an ammonium cation, ammonium substituted with 1 to 4 alkyl or hydroxyalkyl radicals containing from 1 to 5 carbon atoms or a phenyl radical, or a cation of a metal from the group consisting of alkali metals, alkaline earth metals, zinc, manganese, copper ( I) and (II), iron, nickel and aluminium, and n is an integer corresponding to the valence of M. 2. Fungicidal preparations as stated in claim 1, characterized in that R is an optional monohalogenous alkyl radical containing from 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. 3. Fungicidal preparations as stated in claim 1, characterized in that R is an alkoxyalkyl radical containing from 2 to 3 carbon atoms, or stands for a propargyl radical.%4. Fungicidal preparations as stated in claim 1, characterized in that the active material is selected from the group consisting of sodium O-ethylphosphonate, calcium O-ethylphosphonate, aluminum O-ethylphosphonate, magnesium O-ethylphosphonate, zinc O-ethylphosphonate, cuprous O-ethylphosphonate, cupric O-ethylphosphonate, sodium O-isopropylphosphonate, calcium O-isopropylphosphonate, aluminum O-isopropylphosphonate, magnesium O-isopropylphosphonate, zinc O-isopropylphosphonate, cuprous (I)-O-isopropylphosphonate and cupric (II)-O-isopropylphosphonate.