DE2614666A1 - SYSTEMIC FUNGICIDE MIXTURE AND THEIR APPLICATION - Google Patents

Description

DR. BERG DII ^J L.-1NG. STAPF DIPL.-ING. SCHWABE DR. DR. SANDMAIR

PATENT LAWYERS

8 MUNICH 86, POST BOX 86 02 45

26H666

Lawyer File: 26882

APR. 1376

PRODUITS CHIMIQUES UGINE KUHLMANN Paris / France

Systemic fungicide mixture and its application

The invention relates to systemic or systemically acting fungicide mixtures which can be obtained directly by synthesis from by-products or waste products obtained in the manufacture of toluene dxisocyanates'.

There are already systemic fungicides of the benzimidazolyl carbamate family known. In particular, U.S. Patents 2,933,502, 2,933,504, and 3,010,968, issued Feb. 12 1958, on August 10, 1959 and on November 25, 1959, respectively, described a number of products belonging to this family belong. More recently have a number of patents

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8 Munich 80, Mauerkircherstraße 45 Banks Bayerische Vereinsbank Munich 453100

Telegrams: BERGSTAPFPATENT Munich Hypo-Bank Munich 3892623

TELEX: 0524560 BERG d Postscheck Munich 65343-808

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demonstrates the possibilities of using these products or products which belong to the same chemical family, as can be seen, for example, in French patents 1,544 and 1,523,597, filed on November 14, 1967 and May 5, 1967, apply.

The disadvantage of these products is that they are made from pure chemical materials, especially pure ones o-Phenylenediamine must produce, which is relatively expensive and often difficult to produce.

It is also known that the toluene diisocyanates can be used thereby can be prepared by dinitrating toluene, reducing the dinitro derivative to form a crude mixture of toluenediamines, those generally of the o-toluenediamines contained therein is freed, which is achieved, for example, by fractionation (separation of the top fractions) before the material subject to the further procedural steps.

The fraction rich in o-toluenediamines is a by-product (S) that is difficult to utilize.

This by-product, which is indeed available in considerable quantities, consists of more or less impure mixtures of residual toluenediamines, which are most frequently separated off as first runnings in the distillation of m-toluenediamines. The composition of the material can vary widely, _n 809843/1188

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wherein it generally contains more than 90% of a mixture of 2 ₇ 3-Dxaminotoluol and 3,4-diaminotoluene as are present as further components predominantly 2, 4-diaminotoluene and 2,6-diaminotoluene. The ratios between the 2,3-isomer and the _3f4 -isomer differ depending on the manufacturing process used and the distillation conditions used. In general, the concentration ratio between the 3,4-isomer and the 2,3-isomer is between 1 and 5, and it is often between 1 and 3.

The subject of the invention is now a systemic or systemic active fungus inhibitor (M), which is characterized in that it consists essentially of compounds (I) of the formulas

CH Ρ

(a) and (b) ι 3 | 2

'"Χ V

- 8 - CO R (a)

2.1

and

- Ij ³ - cq r * ^b)

2 1

and compounds (II) of formulas (c) and (d)

- N - CO R (c) 2 1

and

R D

NI ³

^X C- - N - CO_R - {d)

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consists in what

Typically a low molecular weight alkyl group with 1 to 5 carbon atoms ,

Rp and R. ,, which can be identical or different, hydrogen atoms or one of the groups of the following formulas -CO-R ₄ , -CO ₂ -R ₄ , -CO-N R ₄ R ₅ / -CH ₂ -N RgR ₇ in which R ₄ and R _{5 are} hydrogen atoms, alkyl, alkenyl or alkynyl groups with 1 to 10 carbon atoms, cycloalkyl, phenyl or naphthyl groups with 5 to 10 carbon atoms, optionally with alkyl groups with 1 to 5 carbon atoms are substituted, where the groups R- and R- may be substituted with halogen atoms, such as chlorine atoms or bromine atoms, and heteroatoms such as nitrogen atoms, oxygen atoms and sulfur atoms, and where the groups R ₄ and R ₅ also oxygen-containing, nitrogen-containing and sulfur-containing heterocycles may contain, and R ₆ and R ₇ , which may be identical or different, represent hydrogen atoms or low molecular weight alkyl groups with 1 to 5 carbon atoms,

wherein the fungicide mixture (M) by dinitration of toluene, reduction of the dinitro derivative to form a mixture of Toluylenediamines, separation of the process by-product (S),

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which preferably contains at least 90% by weight of a mixture of o-tolylenediamines, from the tolylenediamine mixture and converting the by-product (S) to the fungicide mixture (M) using any suitable method and starting produced from the o-toluenediamines of the by-product (S) will.

One can also start from a by-product (S) which contains less than 90% by weight of 0-toluenediamines, in which case the economic benefit of the process is lower.

According to the nature of the groups R ₂ and R-, the number of main products present in the mixture can decrease from four to two, depending on the equilibria that prevail between certain products of this type. Thus, the mixture contains only two isomers when the groups R ₂ and R represent hydrogen atoms.

The concentration ratio between the compounds (II) and (I) is between 1 and 5, more often between 1 and 3, and is close to that of the o-toluenediamines used as starting material.

The mixture according to the invention has the advantage that it is a systemic fungicidal agent which is equally remarkable As effective as the pure products of the benzimidazolyl carbamates described above, without it being used for manufacture of the material is required to isolate some pure chemical product. At the same time allows the mix 238.0. 6 0 9843/1168

the further advantage that it can be made from a by-product that has been difficult for several decades is to be exploited.

The invention thus represents an enrichment of the technology, since it can be produced in a particularly economical manner Provides mixture that is of great practical value in agriculture.

For example, a preferred mixture (M) according to the invention contains the compound of the following formula III as the main component

(III) -NH- CO ₂ CH ₃

as well as a substantial percentage of the compound of Formula IV below

_n CH ₀ ^(IV) sy 2 3

i \

and, as the applicant's studies have shown, has as good a fungicidal effect as the corresponding one on the benzene nucleus non-methylated derivative, the inventive Mixture shows no phytotoxicity for the treated crops.

As already mentioned, various methods are suitable for the by-product (S) based on the 238.0 contained therein.

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o-Toluylenediamines, to be converted into the fungicide mixture (M), so that various suitable methods can be used in the present invention. For explanation and without a final list several of these methods are explained below:

The mixtures according to the invention can by a number of Reactions are obtained which have already been described. The first stage leads to a mixture of benzimidazolyl carbamates, which carry a methyl group on the aromatic nucleus. In particular, it can be carried out using the methods described in US Pat. No. 3,010 procedure described are carried out by according to the reaction (1) given below, the crude or Distilled mixture of the toluenediamines with the reaction product of methylthiourea and an alkyl chloroformate implements:

y \ 5CH

(1) CH-JQ * + R üco- NH - C = N - CO R

Q + R üco- NH - C = N - CO R V "2 ^{2 1}

C - NH-CO ₂ R ₁ + CH -.SH + NH - CO R

in which R _{1 has} the meanings given above.

This first stage can also be carried out using reactions (2 and 3) given below, in which

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the mixture of the toluenediamines with a reaction product from cyanamide and an alkyl chloroformate:

H
I.

NH.

C-NH-CO ₀ R ₁ + NH CO R

ι, c. Λ C. C. Λ

These reactions are described in particular in FR-PS 1 544 474 and HU-PS T 2820, which was filed on July 1, 1970 are.

The mixtures obtained during this first stage unfold in turn interesting systemic fungicidal effects. They can still be converted into other interesting mixes be, for example by reaction with one or more moles of chloroformic acid ester (according to the in the following

given reactions 4 and 5):

co β

(4) CH-JOl C-NH-CO R + ClCO R-) CH-IQ] C-NH-CO ₂ H ₁ + HCl

CO R! 24

CO R • j 2 A

00.Π _Λ \ j 2 4

+ HCl

wherein R- and R- have the meanings given above. These

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Reactions are described, for example, in US Pat. No. 2,933,504.

Further mixtures according to the invention are obtained by reaction the mixtures formed in the first stage with isocyanates according to reaction (6):

(β, "If f ° -" HR ₄

-KU
CHd-Oi C -NH-CO ₂ R ₁ + R ₄ WCO- ^ CH- _TU | _C-NH . _{C0 R}

where the groups R .. and R. have the meanings given above and the reaction can be carried out according to the procedure described in FR-PS 1 523 597.

Further mixtures according to the invention can be prepared by reacting the products obtained in the first stage with carbamoyl chlorides in accordance with reaction (7) given below: / ^R 4 H CO-N

I · ■ I Rc

• R

/ 4

C-NH-CO R + ClCON '^ CH -J- Q C-NH-CO R + K

^ ₁ ν • 3 {^ ~ - - ₂ 1

wherein R ₁ , R. and R ₁ . have the meanings given above. This reaction can be carried out according to the procedure described in FR-PS 1,523,597.

Further mixtures according to the invention can be produced by 238.0.

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that the products obtained in the first stage according to the reaction (8) given below with formaldehyde and a secondary amine converts:

CH -N

N · Λ

C-NH-CO R + CH O + HM -4CH // 2 1 2 \ '

C-NH-CO R + H 0 2 1 2

wherein R., Rg and R_ have the meanings given above.

The mixtures according to the invention are fungicides which are systemically, act against spores and sterilize the mites' eggs.

They enable the control of certain fungal parasites in crops, using a dose which does not in any way damage the plant being treated, namely the foliage nor the plant stalks, the roots or the seeds.

The mixtures according to the invention have the peculiarity that they penetrate the treated plants, either naturally, d. H. over the roots, or over those lying in the air Organs or seeds. They are then promoted with the ascending cell sap and in apoplastxschem ways and in in this way evenly distributed throughout the plant, even in those organs that are only formed after the treatment. The products are known as endotherapeutic products because they make the plant resistant to the entirety of a group

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pe of parasite fungi that belong to a well-defined group.

The mixtures according to the invention thus enable control of mushrooms of the following species:

Fusarium Monilia

Botrytis sclerotinia

Rhizoctonia Coccomyces

Alternaria Aspergillus

Penicillium Helminthosporium

Erysiphe Rhizopus

Cercospora Colletotrichum

Ustilago Verticillium

Phomopsis Sphaerotheca

Venturia Podosphaera üncinula

The mixtures according to the invention have the peculiarity that they enable the control of Ustilago maydis by preventing the fungus from being the organs of distribution To develop sporidia, so that the mixtures are to be addressed as acting against spores.

Finally, the mixtures according to the invention, their The main effect is to destroy the parasite fungi, also a highly beneficial effect on mite eggs which they sterilize. This feature is of particular advantage there

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you can fight two very different types of parasites with a single treatment.

The mixtures according to the invention can be in any one of Formulations that are used for plant protection products are available. These are solutions, suspensions, Emulsions, dust powders, wettable powders, pastes, granulates or aerosols.

For this purpose, liquid solvents can be used, for example aromatic hydrocarbons such as xylene, benzene, toluene or alkylnaphthalene; chlorinated aromatic or aliphatic Hydrocarbons such as chlorobenzene, 1,1,2-trichloroethane or Methylene chloride; aliphatic hydrocarbons such as cyclohexane or paraffins or petroleum fractions; Alcohols such as butanol and glycol and their ethers and esters; Ketones; and polar solvents such as dimethylformamide or dimethyl sulfoxide.

One can use diluents such as water or liquefied gases that are in gaseous form at normal temperature and at normal pressure Condition and used in aerosol spray cans as a propellant. Certain halogenated Hydrocarbons are used, such as "Freon".

Fillers such as chalks, silicon dioxide, kaolin, clay, talc or diatomaceous earth can be added to the solid formulations.

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Finally, surfactants are used, either to ensure a more homogeneous dispersion of the active ingredient in the To achieve diluents, or the wetting power of the formulation towards the plants, their adhesiveness and to increase their lifespan.

The mixtures according to the invention can also be obtained by mixing with other active ingredients, such as fungicidal, herbicidal, insecticidal, acaricidal, bactericidal or nematocidal agents can be formulated.

The formulations contain between 0.5 and 90% of those described Active ingredients.

The substances are used according to methods known per se by dusting, spraying, wrapping, injection, evaporation or aerosol treatment.

The ready-to-use preparations can, depending on the type of application have the following content:

10 to 100 g / 100 l for spray solutions;
10 to 50% for treating the seeds; 90 to 95 kg / 100 l when applying using very small volumes.

To treat the soil, 10 to 200 g of the active ingredient ^{are introduced per m 3 of soil.}

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The following examples serve to further illustrate the invention.

Manufacture of the products :
example 1

Dissolve 20.6 parts by weight of Ν, Ν ¹ -bis (carboxymethyI) -S-methylisothiourea in 1000 parts by volume of an ethanol / water mixture (50/50). Then 7 parts by volume of acetic acid and finally 13 parts by weight of a mixture of toluylenediamines which contain about 70% of the 1,3,4 isomer, 25% of the 1,2,3 isomer and a total of 5% of the 1,2 , 4- and 1,2,6-isomers. The reaction mixture is refluxed for 5 hours. After cooling, it is filtered, washed in the cold with alcohol and the product is dried. This gives 16 parts by weight of a mixture having a melting point of about 250 ⁰ C, which according to the NMR spectrum, approximately 70 to 75 wt .-% 2-carboxymethylamino-5-methyl-benzimidazole (II) and about 25 to 30 weight .-% 2-carboxynethylamino-4-methyl-benzimidazole (I) contains.

C - WH - CO CH

{II}

C - WH - CO CH

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Example 2

A reaction vessel with a capacity of 6000 parts by volume, which can be operated under nitrogen, is charged with 3670 parts by volume of an aqueous solution containing 550 parts by weight of cyanamide. 30 parts by weight of 45% strength sodium hydroxide solution are added to this solution in order to bring the pH to 7.5. While maintaining a pH-value between 7 and 8 which strength by progressive addition of 1175 parts by weight of 40% Natrxumhydroxidlösung is reached, are added at a temperature between 40 and 55 ⁰ C gradually in the course of 1 hour and 10 minutes 1400 parts by weight of methyl chloroformate. After the reaction has ended, the reaction mixture is transferred to a reaction vessel with a capacity of 10,000 parts by volume. The pH is adjusted to a value between 3.9 and 4.1 by the progressive addition of 240 parts by weight of concentrated hydrochloric acid. 1470 parts by weight of a mixture of tolylenediamines are then added, which contains about 55% by weight of the 1,3,4 isomer, 40% by weight of the 1,2,3 isomer and a total of 5% by weight containing 1,2,4 and 1,2,6 isomers. The reaction mixture is heated to reflux and the pH is maintained between 2.5 and 3 by the progressive addition of 1700 parts by weight of concentrated hydrochloric acid. After a reaction time of 1 hour, the mixture is cooled and the precipitate obtained is filtered off. After washing with water and drying, 2050 parts by weight of a mixture are obtained which decompose at 240 to 245 ° C

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melts. The NMR analysis shows that this mixture consists of about 55 to 60% by weight of 2-carboxymethylamino-5-methyl-benzimidazole (II) and about 40 to 45% by weight of 2-carboxymethylamino-4-methyl-

benzimidazole (I).

C - NH - CO CH
²

(II)

-NH- CO CH
²

(D

The yield is about 90%, based on the o-toluenediamines fed to the reaction.

Example 3

A reaction vessel is charged with 120 parts by volume of dry Chloroform, 5.2 parts by weight of the mixture obtained in Example 2 and 2.9 parts by weight of n-butyl isocyanate.

After stirring for 20 hours at 20 ⁰ C, the solution obtained is evaporated after filtration to dryness .. The residue was washed with hexane and dried in vacuo. 7 parts by weight of a solid product are obtained, the NMR analysis of which shows that it is a mixture of about 60% by weight of 2-carboxymethylamino-3-N-butylcarbamoyi-5-methyl-benzimidazole (II) and about 40% by weight % Is 2-carboxymethylamino-3-N-butylcarbamoyl-4-methyl-benzimidazole (I).

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CH CO-NH-C H 3 {4 9

C - NH - CO CH 2 3

CO - NH - C H i 4 9

C - NH - CO CH

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cn

Use of the products:

Example 4

Action of the active substance on the growth of the mycelium.

The nutrient medium according to Czapeck, which has the following composition, is used as the nutrient medium:

Sodium nitrate 2 g

Bipotassium phosphate 1 g

Potassium chloride 0.5 g

Magnesium sulfate (heptahydrate) 0.5 g

Iron sulfate (heptahydrate) 0.01 g

Sucrose 30 g

Agar-agar 15g

Water to 1000 ml

The diluted solutions of the active ingredient are incorporated into this medium, which is melted at 45 ° C., by dispensing a volume of the diluted solutions are used per 10 parts by volume of the nutrient medium.

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The procedure is such that the final concentrations of the active ingredient in the nutrient medium are as follows:

C 0 = 0 ppm (comparison

C 1 = 0.1 ppm

C 2 = 0.4 ppm

C 3 = 1.6 ppm

C 4 = 6.4 ppm

The medium is then placed in Petri dishes with a diameter of 90 mm, after which it is allowed to cool and solidify. Each Petri dish is inoculated with mycelium fragments, taken from fungal cultures with an age of 8 days. The mushrooms are:

Fusarium roseum

Rhizoctonia solani

Phomopsis viticola.

The Petri dishes are incubated for 2 days in a climatic chamber which is kept at 22 ^° C. and a relative humidity of 70%.

After 2 days the mycelium has developed and forms circular mycelial areas around the vaccination site. One measures that Diameter of these mycelial areas and gives the results as a percentage of the diameter of the mycelial areas that are in 238.0.

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the untreated Petri dishes.

O% mean total activity and

100% the control state, d. H. zero activity. The results obtained are shown in Table I below .

Effect on mycelial growth

mushrooms

Fusarium roseum

Phomopsis vitticola

Rhizoctonia Solani

\ j $ oncentra-

product

0.1 0.4 1.6 6.4 0.1 0.4 1.6 6.4 ppm ppm ppm ppm - ppm ppm ppm ppm

0.1 0.4 1.6 6.4 ppm ppm ppm ppm

Examples

No. 3 1 00 75 1 90 00 1 7th 70 1 3 3 3 1 00 1 00 1 00 44 No. 2 67 67 80 0 66 27 3 3 1 00 1 00 95 35 control 00 1 00

Example 5 Inhibition of spore germination

The same nutrient medium is used as in Example 1 (Czapeck medium) and works in the active ingredient in the same way.

The final concentrations in the nutrient medium are as follows:

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CO = O ppm (control)
C 1 = 7.5 ppm

C 2 = 15.0 ppm
C 3 = 30.0 ppm

C 4 = 60.0 ppm
The medium treated in this way is placed in the wells of microscope slides, after which it is allowed to cool and solidify. The lenticular nutrient medium is inoculated by applying 50 μl of an aqueous suspension of spores of the following species:

Botrytis cinerea

Penicillium expansum

The slides are placed in Petri dishes with a diameter of 15 cm, which are provided with a moist filter paper on the bottom. It is incubated for 24 hours at a temperature of 22 ^° C.

Then one counts the number of not germinated under the microscope Spores, this number being taken as a percentage of the total number of spores counted.

0% means that all the spores have germinated, which is also true for the control sample;

while 100% means that no spore has germinated, so that product has had a total effect.

The results obtained are shown in Table II below.

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Table II Percentage of non-germinated spores:

Botrytis cinerea

Penicillium expansum

"■ ^ Concentration product \

7.5 15 30 60 ppm ppm ppni

7.5 15 30 60 ppm ppiu ppm ppm

Example 2 Example 3 Control

5 10 100 100 90 95 100 100 0

65 80 98 100 80 100 100 100 0

Example 6 Effect on spore germination investigated with the help of the inhibition

zone method

An agar-agar-containing nutrient medium (Czapeck) is prepared, which is melted and into which fungal spores are incorporated. This inoculated Medium is poured into petri dishes with a diameter of 10 cm, in which it solidifies.

Then one prepares product suspensions, which one in amounts of 10 μΐ on filter paper discs with a diameter of 0.4 cm. These discs are placed on the surface of the agar-agar medium hung up. The active ingredient diffuses into the medium, in which it inhibits the germination of the spores, so that it settles around the disc around result in areas referred to as "zones of inhibition".

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In the following Tables III and IV the diameters of these inhxbation zones are given, which are associated with Penicillium expansum and Botrytis eineea were obtained.

diameter 3
1 dose 3
2 0 Table III in cm Table IV 0.16 µg 0.4 µg 1 μg N) N) 3.1
3.5 3.9
4.0 4.8
4.4 dose of the inhxbation zones Penicillium expansum Botrytis , 064 µg 1 ppm cinerea product ,1
, 0 0.5
0.6 I 0 ppm 100 ppm example
example 1.0
1.5 1.7
2.1 1000 ρ; 2.1
2.5 product example
example

Example 7 Combating barley rotten mold

Aqueous active substance suspensions are prepared with the following concentrations ;

CO = Og / 100 1 (control)

C 1 = 0.156 g / 100 l

C 2 = 0.625 g / 100 l

C 3 = 2.5 g / 100 l

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C 4 = 10.0 g / 100 l.

These suspensions are sprayed onto barley plants (Rika) which are grown in 250 ml pots and are 12 days old.

The spraying is carried out in such a way that the amount of liquid applied per unit surface area of the pots is in a dose of 1000 l / ha is equivalent.

24 hours after the treatment, spores of Erysiphe graminis are dusted on the leaves of the barley and the plants are kept in a greenhouse at 22 ^° C. for 7 days.

Count the number of rotten mold spots on the first sheet off, this number reflecting the degree of infestation, which is given as a percentage of the degree of infection of the control plants will. Here, 0% means that no disease whatsoever and 100% that the plants are just as severely infected as the control plants. The results obtained are summarized in Table V below.

Table V

Barley Rotten Shrimp Control - Percentage of Infestation Compared to the control plants ________ ^ _

concentration

Products

Erysiphe Graminis
1.56 ppm 6.25 ppm 25 ppm 100 ppm

Example 3 Example 1

100 100

80
100

10 70

0 0

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Example 8 Investigation of the systemic effect

A nutrient solution is prepared for a water culture (solution according to Hoagland & Harnon No. 1 with a pH value of 6). With this Solution, active substance suspensions of the following concentration are prepared:

C = 100 ppm.
These suspensions are placed in test tubes into which a barley plant (rika) with roots is introduced which is 8 days old. The roots are immersed in the liquid. The mixture is left these plants for 2 days in a climate chamber at a temperature of 22 ⁰ C and a relative humidity of 70%.

Subsequently, one prepares an agar-agar medium after Czapeck (see Example 1), in which one at 50 ⁰ C spores of Penicillium expansum incorporated. The inoculated nutrient medium is poured into Petri dishes with a diameter of 9 cm.

Then plant fragments with a length of 0.5 cm are removed from the barley plants (rika), whereby:

from area 1 the tip of the sheath, from area 2 the middle of the first leaf and · ■ takes the middle of the second sheet from area 3.

These fragments are placed in the Petri dishes and on the surface of the agar-agar medium, which the spores of

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Contains Penicilliura expansum.

If the product is a systemically acting material, it can be found in the exuded cell sap of the Cell fragments arranged in this way. This juice wets the surface of the nutrient medium so that the active ingredient can penetrate and can inhibit the germination of the spores of Penicillium expansum, resulting in a plant fragment surrounding area, referred to as the "zone of inhibition".

The presence of these zones of inhibition makes it possible to determine whether the product is a systemically acting product, d. H. a product that enters the cell sap cycle penetrates the plant.

The diameter of these zones shows that there is a relationship between this value and the active ingredient concentration of the initially used There is a nutrient solution in which the roots of the barley plant have been immersed. This determination is made three Days after applying the plant fragments to the agar-agar medium.

The results of this investigation are summarized in the following Table VI, the numerical values for the obtained The diameter of the inhibition zones is in cm.

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Table VI

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Investigation of the systemic effect Diameter of the zones of inhibition

product 3
2 Area 1 Area of extraction
fragments the plant 4th
3.2 Area 2 Area 3 example
example 2.0
3.3 3.6
2.7

Example 9 Combating Erysiphe graminis by treating the soil

Aqueous product suspensions are prepared with the following concentrations :

CO = O ppm (control)

C 1 = 6.4 ppm

C 2 = 16 ppm

C 3 = 40 ppm

C 4 = 100 ppm

Barley (rika) is grown in 250 ml pots. When the plants have reached an age of 8 days, you work in the soil contained in the pots 5 ml of an aqueous active substance suspension a.

24 hours after the treatment, the

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Barley plants by dusting with Erysiphe graminis spores, the rotten mold, and 6 days after this infestation counts the number of rotten mold spots that appeared on the first one Leaf of the plants are present.

This number allows an assessment of the infestation as a percentage compared to the control plants is indicated, with 0% for the non-occurrence of a disease and 100% for the The case is that the plant is just as severely infested as the control plant.

This study shows that the active ingredient after absorption or after it has passed through the roots of the in the treated Plants grown in the soil are absorbed, penetrate the cell sap cycle and the plant becomes resistant to Erysiphe graminis gives. The active ingredient therefore acts on an endothermic route.

The results obtained are shown in Table VII below .

Table VII

Fight the barley rotten mold by sprinkling the ground ! Degree of infestation, expressed as the percentage of infestation on the control plants

Mushroom Erysiphe graminis

concentration

_ 6.4 ppm 16 ppm 40 ppm 100 ppm

product

Example 3 100 100 90 48

Example 1 100 90 70 50

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Example 10 Combating Erysiphe graminis by treating the seeds

Contrary to what was stated at the beginning of the examples, in this study the active ingredient becomes a dusting powder formulated using talc as filler. The concentrations of active substances used are as follows:

C 0 = 0% (control)

C 1 = 0.78%

C 2 = 3.12%

C 3 = 12.5%

C 4 = 50%

Groups of barley seeds (rika) are treated using 200 g of the prepared powder per hundredweight of the seeds and stir for 1 1/2 hours.

The treated seeds are sown in 250 ml pots and placed in a greenhouse. 8 days later, the washed ones are infected Plants by dusting them with spores of Erysiphe graminis, which causes rotten mold. .

After an incubation period of 6 days, count the number of rotten mold spots on the first leaf of each plant available. In this way, the extent of the infestation is determined, which is stated as the percentage of infestation on the control plants is. Here 0% means that the plant does not have a single rotten mold, while 100% means that the plant is as badly infested as the control plants.

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This investigation shows that the active ingredient surrounding the seeds penetrates the plant, is carried away by the cell sap and gives the plant resistance to Erysiphe graminis. The results obtained are shown in Table VIII below compiled:

Table VIII

Extent of infestation by Erysiphe graminis ,

% Rate of infestation of the control plants graminis 50% 12.5% 0
0 mushroom Erysiphe 20th
25th product 0.78% 3.12% Example 3
Example 2 100 40
100 38

Example 11 Effect on cercosporiosis of sugar beet

Aqueous active substance suspensions are prepared, which are used in amounts of 1000 1 per ha applies in such a way that the following application doses result:

DO = O g / ha (control)

D 1 = 150 g / ha

D 2 = 300 g / ha

The treated plants are single-germ sugar beets Ceres, with an age of 2 months, the outdoors

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Field are drawn.

24 hours after the treatment, the beets are infested by spraying on a suspension of Cercospora spores
beticola, which contains 30,000 spores / ml.

25 days after this infestation, the number of spots present on 5 leaves is counted, which are statistically selected from each plot. The results given in Table IX below illustrate the number of spots per sheet. The number 0 indicates that the product is completely active
and works against the nesting of the disease.

Table IX

Effect on sugar beet cercosporiosis

Number of spots per sheet

Product 150 g / ha 300 g / ha

Example 3 0 0

Example 2 0 0

Control 258.5

Example 12 Effect against the germination of spores of üstilago maydis

The active ingredient is diluted with water and added to 1 ml of this
Dilute 1 ml of a suspension of Üstilago maydis spores, proceeding in such a way that the following active ingredient concentrations

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achievements:

CO = O ppm (control)

C 1 = 0.8 ppm

C 2 = 3.1 ppm

C 3 = 12.5 ppm

C 4 = 50.0 ppm

One drop of this treated suspension is applied to the wells of microscope slides in Petri dishes are arranged with a diameter of 15 cm, the bottom of which is covered with a damp filter paper. Then you store them Petri dishes for 24 hours at 22 ° C. Then count the number of spores formed by the germinated spores under the microscope Sporidia. The result is given as the percentage of the number of sporidia that were removed from the untreated control spores were formed. 0% means that the number of sporidia formed is identical to that of the controls and 100% that the treated spores have not formed any sporidia. The results obtained are in the Table X below.

Table X

effect on the Spore formation by Ustilago maydis 50 ppm mushroom Ustilago maydis product itrat:
^ - • ^ Lon 0.8 ppm 3.1 ppm 12.5 ppm

Example 3 100 100 100 100

Example 1 100 100 100 100

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Example 13 Effect against Botrytis cinerea on grape berries

Grape berries (Graisse graft) are treated by immersion in aqueous active ingredient dispersions. These berries are subsequently treated with a drop of conidia suspension that is applied to the injury site that passes through the Tearing off the stem has formed.

7 days after infestation, each berry is rated using the the following assessment criteria:

0 = healthy berry

1 = weak browning in the vicinity of the

Inoculum

2 = browning at 1/4 of the berry

3 = More than half of the berries turn brown

4 = 3/4 of the berry turning brown

5 = browning of the entire berry

The results are summarized in the following Table XI:

Table XI Effect against botrytis on grape berries

Active ingredient concentration / g / 100 Ij Overall rating Average rating

per berry

Example 3 30 120 2.4

Example 1 30 90 1.8

Control - 240 4.80

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Example 14 Effect against mite eggs

The active ingredient is diluted with water so that the following active ingredient is obtained concentrations reached:

CO = O ppm (control)

C 1 = 31.2 ppm

C 2 = 125.0 ppm

C 3 = 500.0 ppm

Bean plants are infested with an age of 15 days with two expanded cotyledons with female mites of the species Tetranychus urticae. One uses pro Sheet 15 female animals. They are removed 24 hours later female animals again, so that only the clutches remain on the leaves.

The beans are then treated by spraying the top and bottom of the leaves with the active compound dilutions given above. The spray is applied in such a way that the liquid begins to trickle down onto the sheet.

15 days after the treatment, count the number of Beans from existing live mites. The difference between the number of individuals found on the control animals and those present on the treated plants gives an indication of the effect achieved by the active ingredient Population decrease. This reduction is given as a percentage of the total population of the control plants, with 0% stands for the fact that the active ingredient has no effect whatsoever, while 100% stands for complete activity. The he-238.0.

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The results obtained are given in Table XII below.

Table XII based on the con- Percentage of mobile population, troll population urticae (Mites) ~~~~ ^ - ^^ concentration Tetranychus 125 ppm 500 ppm Product "" "" "" ■ «w 31.2 ppm 25th
26th 80
70 Example 3
Example 2 10
5

Example 15

Effect against Venturia inaequalis, the cause of apple scab

The active ingredient is diluted in water so that a suspension with a concentration of 30 g / 100 l is obtained. With this suspension you spray apple trees (white cantapple), spraying once every 15 days. 45 days after the first treatment one assesses the extent of the involvement through the use of Scabbed leaves. The results obtained are as % Rate of reduction in the extent of the referral in relation to the controls indicated. 0% means that the Befa ^ is identical to that of the contro ^ p ^ anZen, while 100% means that the product is very effective and the Befa ^ Nu ^ is. The results obtained are in the following given in Table XIII.

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Table XIII Apple scab

• Rate of control of infestation compared to control

plants

Product concentration in g / 100 1% rate of loading

case reduction

Example 3 30 90

Example 2 30 95

Example 16

Action against Botrytis cinerea on grape berries According to the procedure described in Example 13, the berries are treated with aqueous dispersions which contain different concentrations of the product obtained according to Example 2. The results are given in the same way as those of Example 13. The results obtained are shown in Table XIV below.

Table XIV Effect against Botrytis cinerea on grape berries

Concentration in ppm

Control 125 250 500

Total infestation 93 76 61 250

Infestation per berry 1.86 1.52 1.22 5% rate compared to

the control plants 63.8 69.6 75.6

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Example 17

Effect against bean rust

In this investigation the product of Example 2 is used, which is suspended with the aid of a 5% solution of a surface-active agent (Tween 20). The set dilutions of the active ingredient as ppm are the following:

D- = 15.6 ppm

D ₂ = 62.5 ppm

D ₃ = 250.0 ppm

D ₄ = 1000.0 ppm

The suspensions are placed on bean leaves of the "Plein Ie panier "with an age of 10 days sprayed on in such a way that that results in a dose of 1000 l / ha. 24 hours later, the plants are infected by spraying on spores from "Uromyces phaseoli".

Twelve days after the treatment, the extent of the infestation is assessed by assessing the symptoms that are similar to those of the untreated Compare control plants. A scale from 0 to 100 is used, with the rating number 0 for the uninfected Plant stands, while the rating number 100 stands for that the plant is as badly infested as the control plants.

The results obtained are shown in Table XV below .

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Table XV Effect against bean rust

"" ^ - ^ concentration extent of the infestation (%) Control = ppm 100% ppm Product "" "" -. , "^ 15.6 ppm 62.5 ppm 250 , 2 1000 Example 2 93 53 5, 0

Example 18

Effect on growing grain - rust control The product of Example 2 is formulated into a wettable powder which contains 50% by weight of active ingredient, 4.5% by weight of surfactant, 1.5% by weight of silicon dioxide and 44.0% by weight of active ingredient. -% contains kaolin.

This powder is suspended in water so that an active ingredient concentration of 30 g / 100 l is achieved. A cereal plantation ("Talent") in stage 10-5 (in which the last leaf is unfolded) is treated with the aid of the above-described aqueous suspension, which is applied in an amount of 1000 l / ha. Each treated plot with an area of 60 m ² is treated four times. Four untreated plots are used as control plots. In the treatment 20 days later, the degree of infestation of the grain by yellow rust (Puccinia striiformis) is assessed using a scale from 0 to 100 on four samples from 100 stems taken per plot. The rating number 0 stands for no infestation and the

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Score 100 for a complete infestation of the leaves through the disease. Towards the end of the cultivation process, the yield in the treated and untreated plots is assessed. The results obtained are shown in Table XVI below.

Table XVI

Control of grain rust. Assessment of the infestation

in the treatment 20 days after the yield in

action hundredweight / ha

Example 2 9.4 7.9 50.5

Control 10.5 19.8 45.7

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Claims (8)

26U666 Claims (λJ. Systemic fungicide mixture (M), characterized in that it essentially consists of compounds (I) of formulas (a) and (b) \ I N - CO R 2 1 Ca) and I ³ N - CH. and (b) Compounds (II) of formulas (c) and (d) CH Π 13 N - (c) and I ² I ³ - N - CO R 2 1 (d) consists in what R _{1 is} a low molecular weight alkyl group with 1 to 5 carbons material atoms and 238.0. 9 84 3/1168 26U666 R ₂ and R ₃ , which can be identical or different, hydrogen atoms or groups of the following formulas - CO - R ₄
-CO ₂ - R ₄ - CO - NR ₄ R ₅ - CH ₂ - NR ₆ R ₇
mean in which R. and R _{5 are} hydrogen atoms, alkyl, alkenyl, alkynyl, cycloalkyl or aryl groups, the groups R ₄ and R ₅ optionally being substituted by halogen atoms and being able to contain heteroatoms such as nitrogen atoms, oxygen atoms or sulfur atoms, and where the Groups R ₄ and R _{5 can} also contain oxygen-containing, nitrogen-containing or sulfur-containing heterocycles and R, and R_, which can be identical or different, water Substance atoms or low molecular weight alkyl groups with 1 to carbon atoms mean, where the fungicide mixture (M) by dinitration of toluene, reduction of the dinitro derivative to form a mixture of toluene diamines, separation of the process by-product (S), which preferably contains at least 90% by weight of a mixture of o-toluenediamines the tolylenediamine mixture, and converting the by-product (S) to the fungicide mixture (M) using any suitable process and starting from the o-toluenediamines of the by-product (S). 2. Mixture according to claim 1, characterized in that the group R _{1 is} an alkyl group with 1 to 5, 238.0. 6098A3 / 1168 26U666 preferably 1 carbon atom and the groups R ~ and R-. Mean hydrogen atoms. 3. Mixture according to claim 1, characterized in that that the group R. is an alkyl group with 1 to 5 carbon atoms, preferably a carbon atom, the group Rp a group -CO-NHR, in the R. for an alkyl group with 1 to 10, preferably 4 carbon atoms, and the Group R ~ mean a hydrogen atom. 4. Mixture according to one of claims 1 to 3, characterized in that the concentration ratio of the compounds of the formula (II) to the compounds of the formula (I) between 1 and 5, and in particular between 1 and lies. 5. Fungicidal agents, characterized in that they contain a mixture according to Claims 1 to 4. 6. Acaricidal agents, characterized in that they contain a mixture according to any one of claims 1 to 4. 7. Use of the mixtures according to claims 1 to 4 for Fight against fungi. 8. Use of the mixtures according to claims 1 to 4 for Control of mites. 609843/1168