DE2056176A1 - Arable and horticultural fungicides - Google Patents

Description

2056176 FARBENFABRIKEN BAYERAG

LEVERKUSEN-Bayerwerk * Q ^ gy _t $ 70 Tatent Department

Agricultural and horticultural fungicides

The present invention relates to new organic phosphoric acid esters with fungicidal activity and their use for combating harmful fungi.

The active ingredients according to the invention, namely organic phosphorus

- 1 - nit 47

1ÖÖ821 / 2285

INSPECtSD

2055176

acid esters, are represented by the following general formula:

/ PS GH ₉ (( ) (I).

2 ' \ - /

Therein "R denotes an alkyl group with 1 to 3 carbon

2
atoms and R is an alkyl group with 1 "to 4 carbon atoms.

From the specification of Japanese Patent Publication No. 2 67 it is known that phosphoric acid dialkylamide thiolates of the general formula

where R is a lower alkyl group and Y is nitro, alkyl, methoxy or nitrile, have fungicidal properties.

It has now surprisingly been found that phosphoric acid monoalkylamide thiolates of the formula (I) have a much higher fungicidal activity than the phosphoric acid dialkylamide thiolate Formula (II).

The compounds according to the invention show a high fungicidal activity against pathogenic bacteria and fungi, the plant diseases cause, and are distinguished by the fact that their activity against bacteria and fungi in a wide range Spectrum is effective. In addition, these compounds are low in toxicity to warm-blooded animals and possess suitable affinity for higher plants. They do not pass any toxicity on to higher plants if you put them in using normal concentrations. Accordingly, the compounds according to the present invention are used as arable crops and horticultural fungicides to prevent or control plant diseases caused by bacteria or fungi be suitable.

In particular, the compounds according to the present invention can be used as fungicides to protect plants

- _ 2 -

109821/2285

• '3 2056T76

Kranfclieiten caused by Arcliimyceteii, Phy corny ce ten, Ascomyceten, Basidiomycetes, Fungi imperfect! or other bacteria and fungi.

The active compounds according to the invention can be used to combat pathogenic bacteria and fungi that live in the above-ground parts of plants against pathogenic bacteria and fungi, which attack the plants from the ground and cause tracheomycosis, as well as against sperm-infectious pathogenic bacteria and Fungi or soil infectious pathogenic bacteria and fungi are applied.

Considering the excellent fungicidal above Properties bring the active ingredients according to the present invention good results when applied to diseases caused by those pathogenic bacteria and fungi that are treated with fungicides as a result of heavy metals contained therein, such as arsenic or mercury Humans and pets are dangerous and must be fought. In addition, they provide in particular in the fight against pathogenic bacteria and fungi that cause diseases in rice plants cause good results. In particular, these compounds show excellent activity against piricularia qryzae, which causes powdery mildew on rice plants, and against Pellicularia sasakii, which causes the disease of the same name, and against Xanthomonas oryzae, which causes the bacterial powdery mildew and they can be used to control these bacteria at the same time. These Compounds show not only preventive but also healing effects and therefore their suitability for simultaneous control is great. In addition, the active ingredients show according to this present invention much better activity than the above analogous phosphoric acid dialkylamide thiolates of formula (II) when applied to the water surface of rice fields be applied.

The compounds according to the present invention show excellent Activity against other bacteria and fungi that infect rice plants or other arable crops, such as e.g. against Ervinia aroideae, the bacterial root rot of China

- 3 10-9 £ 21/22 8 pp

Cabbage causes, Xynthomonas citri, the cancer on citrus fruits causes, Cochliobolus miyabeanus, which causes brown spots on rice, Mycophaerella musicola, which causes leaf spots causes on bananas, Botrytis cineraria, which causes a gray coating on gooseberries and other plants, Plasmopara viticola, which causes powdery mildew on grapes, Glomerella eingulata, the anthracnose on grapes, apples and pears, Sclerotinia sclerotionum, which causes vegetable stem rot, Collectotrichum lagenarium, which causes anthracnose on melons, Diaporthe citri which causes melanosis on citrus fruits, Podocphaera luicotricka, which causes powdery mildew on apples, Sphaerotheca fuliginea, which causes powdery mildew Cucumber causes, Alternaria mali, which causes the cork stains on apples, Alternaria kikuchiuna, which causes the black Causing spots on pears, Venturia inäqualis, which causes the scab on apples and Venturia pirina, which causes the scab on pears.

As described above, the compounds of the present invention show excellent effectiveness in combating Pathogenic bacteria and fungi that damage rice plants and other crops and are particularly common in the Prevents and is effective in curing diseases of rice when applied to the water surface of the rice fields will. Accordingly, the compounds according to the present invention are of great value for arable labor saving.

In addition, there is no problem of the build-up of toxicities on the arable products, since the fungicides are not harmful Contain heavy metals such as arsenic or mercury. It can be seen from this that the compounds according to the present invention Invention as agricultural chemicals have great advantages.

The phosphoric acid monoalkylamide thiolates are new compounds which were made for the first time. These compounds are made in the following manner

- 4 109821/228 5

R ¹ O ^ 0 R ² NH '

(III)

M + Hal OH,

ΪΓΪΪΗ

12th
In this formula, R and R have the same meaning as

in formula (I),

M means an alkali metal or the ammonium residue and shark a halogen atom.

The compounds of the formula (i) according to the invention can easily be prepared by condensation of an alkali metal or an ammonium salt (III) of O-alkyl-N-alkylamidothiophosphoric acid with a corresponding benzyl halide (IV) in an organic solvent. The organic solvent used is preferably aliphatic or aromatic hydrocarbons (which can be halogenated) such as gasoline, methylene chloride, chloroform, carbon tetrachloride, benzene, chlorobenzene, toluene and xylene, ethers such as diethyl ether, dibutyl ether, dioxane and tetrahydrofuran and low-boiling aliphatic alcohols or ketones such as methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone are used. Lower aliphatic nitriles such as acetonitrile or propionitrile can also be used. The reaction temperature varies depending on the kind of the solvent to be used, but the reaction can be carried out in a relatively wide temperature range. Generally, the reaction at 0 - 11O ⁰ C, preferably at 10 - 80 ^0C performed. The preparation of the compounds according to the present invention is illustrated in more detail by the following examples.

109821/2286

Experimental example 1;

300 ml of dioxane was added to a solution of 51 g of potassium hydroxide in 300 ml of water. The mixture was cooled so that the reaction ^{could take place at 30-4O 0} C and 91 g of O-ethyl-N-iso-propylamide-thiophosphoric acid chloride were added dropwise with stirring to the mixture. After the completion of the reaction, stirring was continued for 1 hour, dioxane and water were then distilled off and the residue was dissolved in water, whereupon benzene was added and shaken. The aqueous layer was concentrated and the residue was dissolved in 400 ml of alcohol. The solution was then added dropwise to 57 g of benzyl chloride and the mixture stirred at 7O ⁰ C for 2 hours. Thereafter, the reaction mixture was cooled and the inorganic salt was separated by filtration, whereupon the alcohol was distilled off. The residue was dissolved in benzene, washed with water and 1 $ strength sodium carbonate, then dehydrated with anhydrous sodium sulfate and the benzene was distilled off. Vacuum distillation of the residue gave 103 g of O-ethyl-S-benzyl-N-iso-propylphosphoramid-thiolate of the formula below at 15 mm Hg and 155-158 ⁰ C. Recrystallization from η-hexane and benzene gave white crystals of Melting point of 41.5 - 43 C.

Using the same procedure, the following compounds were made:

1 09821/2285

T from e 1 1 e 1

Connection no

Structure formula Physical characteristics

Melting point (° C / mm Hg)

Refraction

CH ₃ O-

II ►P-S-CH ₂

168-170 / 0.15

(1.5608)

CH ₃ O
C ₂ H ₅ NH

PS-CH ₂ -V / N) 164 -166 / 0.07

(1.5528)

CH ₃ O-CH3CH-NH '

0
ί

'PS-CH ₂

160-16Λ / 0.Ο7 [50-52]

CK ^ -NH

PS-CH ₂

160-163 / 0.15

(1.5510):

C ₂ H ^ -NH

163-166 / 0.1

(1.5Α31) Ι

. 109821/228

Connection no.

Structure formula

Physical characteristics

Melting point refraction =

(° C / mm Hg)

index

/ 2C ( ⁿ D

PS- "CH ₂

155-158 / 0.1. 5-43]

_{CHQ-CH2-CH-NH}

163 -166 / 0.15 (59 - 61}

158-160 / 0.1

(1.5410)

CHo-HH-

CH ₃ CHO CH ₃

CH ₀ CH -KH

CH ₃

PS-CH ₂

[61.5-62.5 yrs

When the compounds are used as fungicides, they are diluted directly with water or after using solvents or auxiliaries have been mixed depending on the use or they are mixed with various inert gaseous, liquid or solid diluents and / or carrier materials, optionally with other auxiliaries such as surface-active agents, Emulsifiers, dispersants, lubricants η and adhesives in

1 0 9 8 2 1/2 2 8 p

conventionally incorporated into the preparation of agricultural chemicals and used in various forms.

Freon or other aerosol propellants, which are gaseous under emergency conditions, should be mentioned as gaseous diluents or carrier material. Liquid diluents or carrier materials are water and organic solvents such as aromatic hydrocarbons such as xylene, toluene, benzene, dimethylnaphthalene, and aromatic naphthas, chlorinated aromatic or aliphatic hydrocarbons, e.g. chlorobenzene, chloromethylene, chloroethylene and carbon tetrachloride, aliphatic hydrocarbons, e.g. cyclohexane and gasoline Paraffin, alcohol, for example methanol, propanol or butanol, ketones, for example acetone, methyl ethyl ketone and cyclohexanone, and polar solvents, for example acetonitrile, dimethylformamide and dimethyl sulfoxide , may be mentioned. Solid diluents or carrier materials include powders of natural mineral substances such as atapulgite, lime, clay, talc, kaolin, montmorillonite, diatomaceous earth and calcium carbonate, or powders of synthetic mineral substances such as highly dispersed silica, aluminum oxide and silicates.

Suitable emulsifiers are nonionic or anionic surface-active agents, such as polyoxyethylene fatty acid esters, polyoxyethylene-aliphatic alcohol ethers (such as, for example, alkylaryl polyglycol ethers), alkylsulphonates and arylsulphonates. Lignin, sulphite waste liquor and methyl cellulose may be mentioned as dispersants. It is possible to add other agricultural chemicals such as insecticides, nematocides, fungicides (including antibiotic substances), herbicides or growth-influencing agents, fertilizers or fertilizing substances as required to the composition . If the compounds according to the invention are used together with 0,0-di-isopropyl-S-13-2-chlorine (or nitro) phenoxy-ethyl-phosphorothiolate, an excellent synergistic, fingicidal effect is achieved.

The fungicides according to the invention contain 0.1 to 95 wt .- ^, preferably 0.5-90% by weight of the active ingredients mentioned. the

1 η ο ri.>! / ■ /? R f ι ■

205-176

Concentration of the active ingredients can vary depending on the intended use and Form of preparation can be changed according to the objects, the time and place of their application as well as depending on the degree of the disease.

The fungicides according to the present invention can be used in any type of preparations that are in the field of agricultural chemicals Are common, as liquids, as emulsifiable liquids, as concentrated emulsions, as wettable Powders, soluble powders, oil preparations, aerosol preparations, pastes, smokable agents, dust, particles, coated particles, tablets, granules and pellets can be applied.

The fungicides according to the invention can be used against harmful insects and / or pathogenic bacteria or in other places where the harmful insects and / or pathogenic bacteria live, directly or using devices after a spray, atomization, atomization, powder atomization, particle atomization, Mixing or smoking, pouring or powder incrustation methods can be used. It is also possible to use the fungicides of the present invention in the so-called "ultra-low spray method". With this method it is possible to increase the concentration of the active ingredients to 95 ^a / o or even to 100 $> . When used, the concentration of the active ingredient in the ready-to-use preparation can vary within a fairly wide range u.zw. for the same reasons as set out for the forms of the preparations, but it is preferred to use the concentration of the active ingredient generally at 0.005 to 10 percent by weight, preferably 0.01-5% by weight. The amount of the fungicides according to the invention is approximately 15 to 1000 g / 10a, preferably 40 to 600 g / 10a, based on the active ingredient. It is possible and often necessary to use fungicides in amounts that are significantly above or below. According to the invention, a fungicidal composition is prepared which is characterized in that it contains a compound of the above general formula (I) and a liquid or a solid diluent and / or a carrier given NaLItJ together with other auxiliaries. Further

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10982 1/2285

BATH

a method for combating fungi is specified, the is characterized in that a compound of the general formula (I) alone or in combination with a solid or liquid diluent and / or carrier material on plants or on places where plants are cultivated, if necessary, applies together with an aid.

The present invention is illustrated by the following examples explained in more detail, but they have no restrictive effect.

Example 1;

15 parts of compound no * 7 according to the present invention, 80 parts of a mixture of diatomaceous earth and kaolin and 5 parts of the emulsifier Runnox (product of Toho Kagaku Kogyo Kabushiki Kaisha) were ground together and mixed into a wettable powder. This was when applying diluted with water.

Example 2;

30 parts of compound no. 3 of the present invention, 30 parts of xylene, 30 parts of Kawakasol (product of the Kawasaki Kasei Kogyo Kabushiki Kaisha) and 10 parts of the emulsifier Sorpol (Product of Toho Kagaku Kabushiki Kaisha) were mixed with stirring to obtain an emulsifiable preparation. This was then diluted with water when used.

Example 3:

10 parts of Compound No. 6 of the present invention, 10 parts of bentonite, 78 parts of zeeklite and 2 parts of lignin sulfonate were mixed, and this mixture was intimately mixed with 25 parts of water. This mixture was then finely divided using an ejector granulator to obtain particles in the size of 375 / u-750 / u, after which drying was carried out ^{at 40-5O 0 C.}

Example 4:

2 parts of compound no. 8 of the present invention,

- 11 -

109P21 / 228B

98 parts of a mixture of talc and clay were ground and put together mixed to obtain a powdery, ready-to-use preparation.

Example 5;

A mixture of 50 % of a 1: 1 mixture of the compound of the formula I of the present invention and 0,0-di-iso-propyl-S-ß-2-chloro (or nitro) phenoxy-ethyl-phosphorothiolate, 20 % of one Emulsifier (alkylaryl polyglycol ether) and 30 % of a solvent (xylene) were stirred and a homogeneous, concentrated, emulsified liquid (emulsion preparation) was obtained. This liquid was then diluted with water (in an approximately 1000-2000-fold amount, based on the volume) and the desired concentration of the active ingredient was obtained. The ready-to-use preparations produced in this way were then sprayed onto the pathogenic bacteria or onto the plants on which they grew with the aid of a spray device.

In comparison to active ingredients of a similar structure that were previously known, the present novel show the invention Compounds significantly improved potency and they have low toxicity to warm blooded animals. Accordingly, the novel compounds of the invention are of great value. Unexpected benefits and excellent effects of the new compounds according to the present invention can the test results as set out below will be removed.

The results of the tests on the effectiveness of the compounds according to the present invention as agricultural chemicals will now be described.

Test 1:

Test for the effectiveness against meltau of rice plants (pot test)

a) Test for preventive effect

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Water rice (Jukokku type) was placed in a 12 cm pot Diameter cultivated and an emulsion preparation in the shoot stage, which the compound according to the invention in a previous

■ z

given concentration was sprayed in an amount of 50 cm / 3 pots under a pressure of 1.5 kg / cm on the pots mounted on a rotating table.

The pots treated in this way were then placed in a damp room at 25 ° C and a relative humidity of 100% for 2 days from the day following the chemical spraying, while which time the rice plants in the pot twice with a suspension of spores of the cultivated pathogenic bacteria were sprayed by powdery mildew.

7 days after the infection, the percentage was determined for each pot of the disease incidence using a scale for the disease incidence from 0 to 5 (see below) and the percentage of the disease infestation of the chemically treated areas, compared to the untreated areas, calculated.

The disease infestation 0 means that no disease occurred in the sample pot and 100 means that the powdery mildew infestation was exactly the same size as an untreated pot.

The phytotoxicity of the chemicals was tested at the same time.

Degree of disease Percentage of areas on which affected the disease. spots appear

0 0 ok

0.5 less than 2 #

1 3 - 5 1o

2 6 - 10 ok

3 11 - 20 io 4- 21 - 4-0. 96

5 more than 40%

b) Test for the healing effect

This test was run to determine the healing properties of the

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10 9 8 2 1/2285

to determine compounds according to the invention in pathogenic bacteria which have infected rice plants and cause diseases. Water rice of the same kind as in test a) was left in a humid room at 25 ^° C. and a relative humidity of 100 % for 2 days, during which time the rice plants were infected with a suspension of cultivated pathogenic bacteria of Meltau by spraying. The next day, the compound according to the invention was applied in the form of an emulsion preparation with a prescribed concentration, namely in one

Amount of 50 ml / 3 pots and a pressure of 1.5 kg / cm, the pots being mounted on a turntable. The degree of disease was then determined on a scale from 0 to 5 similar to the preventive test and the disease infestation ratio calculated by determining the percentage of disease infestation on a sample pot compared to that on the untreated area. A disease infestation ratio of 0 means that no disease occurred in the sample pot and the disease incidence of 100 means that meltau occurred to the same extent as on an untreated area. the Phytotoxicity of the chemicals on rice plants was tested at the same time.

c) Test of effectiveness when applied to the surface of water

Water rice (Asahi type) was planted in a 0.01 m large porcelain pot (5 stems / root) and cultivated in the water-filled stage. In the sprouting stage, an emulsion preparation containing 0.05 % of the compound according to the invention as an active ingredient was injected onto the water surface in an amount of 10 ml / pot (500 g / 10 a, based on the active ingredient) in such a way that the chemical Liquid did not touch the rice plants directly.

The sample rice plants were then kept in a humid room at a temperature of 25 C and a relative humidity of 100 % from the 3rd day after the application of the chemical for 2 days, during which time the rice plants were used twice

- 14 109821/2285

Λ ζ -ιυαο ι / ο

a spore suspension of a meltau culture infected by spraying became.

7 days after the infection, the degree of disease infestation by Meltau in the pot was measured on a scale from 0 to 5, very similar to the preventive test, and the disease infestation was determined by calculating the percentage of disease infestation in the sample pot compared to an untreated pot. So the disease infestation level 0 means that in the sample pot appeared no disease and the disease incidence sgrad 100 that on the sample pot dex disease infestation was just as great as in the untreated plot. The toxicity of the compounds on rice plants was also tested.

The results of tests a), b) and c) are shown in Table 2:

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109821/228 »

Table 2

Test results on the effectiveness against mildew of - rice plants

link
No. Concentration
tion of the
Active ingredient
fes in %
r ■ Degree of disease infestation {%) Healing
'"effect Effective-.
.ness at
use
on the W
water surface Phytoto
xicity
JS- 1 - i - I.
I. - I. - 1 0.Q5 Preventive
gungswir ·
Rung 20th - j i - 2 11 10 12th 3 Il 8th 9 U Λ Il 3 8th 5 Il . 5 6th 18th 6th Ii 5 6th 10 7th Il 0 -12 8th Il 1 8th 9 Il IBP commercial
lich (ver
same) 11 8th 10 18th DBP
(Comparison) Il 12th Untreated
sample 16 ICO ICO 100

- 16 -

109821/2285

Remarks:

1. The connection numbers in the table correspond to those in table 1.

2. The symbol "-" in the "Phytotoxicity" column means that the chemical does not have a disruptive effect on the growth of the rice plants.

3. Each value was an average over the area of 3 pots.

4. IBP: 0,0-di-isopropyl-S-benzylthiol-phosphate.

5. DBP: 0-ethyl-S- (2-methoxybenzyl) -N, N-dimethylphosphoramide thiolate

(The compound is known from Japanese Patent Publication No. 21 499/67).

Test 2:

Test for the effectiveness against Hypochnus sasakii of rice plants (pot test).

Water rice (Kinmau type) was made in an unglazed pot of 12 cm in diameter and cultivated at the primary shoot stage a dilution containing the compound of the present invention in a prescribed concentration on the rice plants as applied in test 1.

The next day, the rice plant roots were infected with the pathogenic bacteria Hypochnus sasakii, which had previously been grown on a barley culture medium for 10 days and had formed a sclerotium. The sample was then for 8 days in a Inokulierkammer at 28 - 30 ⁰ C stored, wherein the relative humidity was greater than 95%. The degree of disease infestation was determined.

The damage rate was determined from the spread of the disease spots calculated from the stem root based on the following formula.

iN-3 + ^ Np + Ν- »+ ^ Damage rate = -2 ^. ! ii_ _x 100

where N is the total number of stems tested

Nq the number of stems on which no disease spots appeared,
N _{1 is} the number of stems on which the disease spots

- 17 1098 21/2285

to the first leaf sheath from the root, reach, N2 the number of stems on which the disease spots

extend to the second leaf sheath, N ₃ the number of stems on which the disease spots are located

extend to the third leaf sheath. The results are shown in Table 3.

Table 3:

Test results regarding the
of rice Active ingredient
concentration
in % Effectiveness against Hypochnus sasakii Phytotoxicity link
No. 0.05 Damaging
rate in % - 5 0.05 28.7 - 6th 0.05 9.4 - 8th 0.05 16.7 - IBP (commercial
common)
comparison 0.008 48.7 brown spots Ulvacid (han
usual)
comparison 6.2 - Untreated
sample 68.4

Remarks:

1. The compound numbers in the table correspond to those in table 1.

2. The value of the damage rate was calculated from the average value of three pots.

3. IBP: 0,0-di-isopropyl-S-benzylthiol-phosphate.

4. Ulvacid: methylarsine-bis-dimethyl-dithiocarbamate.

Test 3:

Test for efficacy against bacterial leaf mildew (bLight) (pot test)

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10 9 8 2 1/2285

A suspension of pathogenic bacteria, with shaking Grown on potatoes for 2 days in a semi-synthetic culture medium was done by injection and by Applied to the central parts of the most highly developed leaf of water rice in the 4th or 5th leaf instar, which is in a unglazed porcelain pot of 12 cm diameter was grown, applied. Three hours after the inoculation, an emulsion preparation of the compound of the present invention was made at the prescribed one Concentration in an amount of 50 ml / 3 pots, under a pressure of 1.5 kg / cm on the turntables mounted Pots applied.

After application, the test plants in a glass greenhouse at 25 were - left 35 ⁰ C and a relative humidity of more than 80% for 10 days. The ratio of the areas on which the disease spots appeared and the total leaf area was examined, and the disease rate (%) was calculated according to the formula given below. The Phy totoxizität of the chemical was also examined. The results are shown in Table 4.

Disease attack degree = x

mean in it

N is the total number of sheets tested,

A is the number of leaves on which the degree of staining is about 5 % based on the total leaf area, "

3 the number of sheets on which this ratio is about 10 % ,

C is the number of sheets on which this ratio is about 20-30 % ,

D is the number of sheets on which the above ratio is about 40-60 % ,

E is the number of sheets on which the above ratio is more than 70 % .

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109 8 21/2285

ZJO

Table 4:

Test result regarding the effectiveness against bacterial leaf meltau of rice plants "

link
No. concentration
of the active ingredient
% Disease
infestation
% Phytotoxic
ity 3 0.05 j 23.4 - 5 0.05 27.0 - 6th 0.05 21.8 - 7th 0.05 17.8 - "Sankel ¹ fuel
powder (h
customary, ¹
same) Z-
at-
\ fei-.
0.1 27.2 tan
stains Untreated
sample - 56.7 -

Remarks:

1. The compound numbers in the table above correspond to those in Table 1.

2. The value of the degree of disease was obtained from the mean of 3 pots.

3. "Sankel" wettable powder: nickel dimethylditiiiocarbamate.

103821/2285 - 20 -

Tabel

Test result se in terms of svnerqistic Healing
effect degree (%) Effects Toxic
activity Active ingredient concentration
of the active ingredient Disease infestation
(Meltau) 10 Effective
at
Water-
surface
chenan-
reversible Disease
infestation level - A. in % Pass
gearing
effect 12th 8th % (Hypochromic
nus sasakii - B. 0.025 + 0.025
= O, o5 0 1000 10 5.0 - Untreated
th sample 0.025 + 0.025
= 0.05 1.5 100 6.0 - 100. 75.0

- 21 -

■ <] cn

Remarks:

1. The tests for effectiveness against Meltau and Hypochnus sasakii were carried out using the same methods as in test la), b) and c) and in test 2 carried out.

2. The active ingredient A consisted of a mixture of the compound no. 6 according to the present invention with 0,0-diisopropyl-S-ß- (chlorophenoxy) ethyl phosphorothiolate (Mixing ratio 1: 1).

3. The active ingredient B consisted of a mixture of compound no. 7 according to the present invention and 0,0-Di-isopropyl-S-ß- (2-nitrophenoxy) ethyl phosphorothiolate (Mixing ratio 1: 1)

- 22 -

109321/22 85

Claims (6)

Claims;
ρ) ¹ phosphoric acid monoalkylamide thiolate of the formula E ¹ O. R ² K in which R ¹ for alkyl with 1 to 3 carbon atoms and R ^{2 represents} alkyl having 1 to 4 carbon atoms, 2. Process for the preparation of phosphoric acid monoalkylamide thiolates, characterized in that compounds of the formula -M (III) in which . 1 2 R and R have the meaning given above and M stands for an alkali metal or the ammonium radical, with benzyl halides of the formula Shark CH ₂ <f \> (IV) in which Hai stands for a halogen atom . - 23 - 0 9321/2285 3. Fungicidal agent, characterized by a content of phosphoric acid monoalkylamide thiolates according to claim 1. 4. A method for combating fungi, characterized in that one phosphoric acid monoalkylamide thiolate according to claim can act on mushrooms or their habitat. 5. Use of phosphoric acid monoalkylamide thiolates according to Claim 1 for combating fungi. 6. Process for the preparation of fungicidal agents, characterized in that one phosphoric acid monoalkylamide thiolate according to claim 1 mixed with extenders and / or surface-active agents. - 24 - 1U3321 / 2285