NL8900641A - PREPARATIONS WITH FUNGICIDE EFFECT. - Google Patents

Description

*

Preparations with a fungicidal effect ^

This invention relates to a fungicidal composition and more particularly to an agricultural and horticultural fungicidal composition having an improved plant disease control effect on plants.

Fungicidal preparations containing tetrachloroisophthalonitrile (hereinafter "TPN") as an active ingredient are known. They are used inter alia to prevent and control fungal diseases of fruit-bearing trees and vegetables and are generally used as a spray for the foliage or mixed.

It is known that compounds of formula I, wherein R is a methoxymethyl, benzyl, chloromethyl, 2-tetrahydrofuryl or 2-furyl group, Z 2-oxo-1,3-oxazolidin-3-yl, 1- ( methoxycarbonyl} ethyl, 2-oxo-thiolan-3-yl or tetrahydro-2-oxo-3-furanyl, a hydrogen or chlorine atom, and also represent a hydrogen or chlorine atom, have excellent, preventive, curative systemic fungicidal activity , in particular to combat downy mildew and epidemic diseases, which cause serious damage to fruit-bearing trees and vegetables.

Many mixtures of TPN or of a compound of formula I with other fungicides have been proposed and used to increase the spectrum of action, enhance activity, or enhance fungicidal activity against resistant strains.

Although the use of a mixture composed of TPN and 2-methoxy-N- (2-oxo-1,3-oxazolidin-3-yl) -aceto-2 ', 6'-xylinide (common name: oxadixyl) has been described in Trans. Br. Mycol.

Soc. 85, 299-306 (1985), it is not suggested in this reference that a mixture of TPN and oxadixyl would have a more than additive (ie synergistic) fungicidal effect. Moreover, the TPN used in this case is used as a wettable powder and the only cited example of the mixture ratio for oxadixyl and TPN is 1: 3.

The present invention provides a liquid formulation (ie an aqueous, concentrated suspension) 8900641; -2- * containing a phenylamide compound of formula I and TPN in the weight ratio of 1: 2 to 1:15 and a surfactant, wherein the solids have a particle size in the range of 0.5 to 5.0 µm (microns) at the 50% volume accumulation point. The last volume medium diameter is hereafter referred to as VMD.

It has been found that the compositions of the invention have a fungicidal effect which is considerably greater than the additive effect that would be expected upon mixing the active ingredients.

The synergistic effect is particularly pronounced in preparations containing a compound of formula I, wherein: R is methoxymethyl, benzyl, chloromethyl or 2-furyl, Z is 2-oxo-1,3-oxazolidin-3-yl, 1- ( methoxylcarbonyl) -ethyl or tetrahydro-2-oxo-3-furanyl, 15 X ^ is a hydrogen or chlorine atom and is a hydrogen atom (hereinafter referred to as compounds of formula la).

Recommended compounds of formula I for use in a preparation according to the invention contain the compound of formula Ia, in which a) R is methoxymethyl, Z is 1- (methoxycarbonyl) ethyl and X ^ is hydrogen (metalaxyl) b) R is methoxymethyl, Z is 2-oxo-1,3-oxazolidin-3-yl and X ^ is hydrogen (oxadixyl) c) R is benzyl, Z is 1- (methoxycarbonyl) ethyl and X ^ is hydrogen (benalaxyl) d) R is Chloromethyl, Z is tetrahydro-2-oxo-3-furanyl and Χ ^ is hydrogen (ofurace) e) R is 2-furyl, Z is 1- (methoxycarbonyl) ethyl and X ^ 30 is hydrogen (furalaxyl) and f) R is methoxymethyl, Z is 2-oxo-1,3,3-oxazolidin-3-yl and X is a chlorine atom.

The most recommended compounds of formula I for use in the invention are metalaxyl and oxadixyl.

No special restriction on the method of preparing or manufacturing the fungicidal composition has been proposed according to this invention. The preparation according to the invention can be prepared or manufactured in a usual manner, 8900641? b -3- for example, according to a method in which the ingredients are mixed and the solid particles thereof are ground to the desired particle size in a suitable grinder.

Examples of grinders suitable for use in the process of the invention include, for example, ball mills, impact type crushers, air grinders, wet type grinders, and so on.

R

The VMD was measured with the Coulter Counter model TA-II (from Kabushike Kaisha Nikkaki). Preferably, the VMD will be in the range of 0.8 µm to 2.5 µm, and it is even more recommended that the VMD be in the range of 0.8 µm to 1.8 µm, especially 0.5 to 1.5 pm ^.

Although the levels of TPN and the phenylamide compound of formula I in a composition of this invention are not particularly limited, it is desirable that the composition should contain 1-98 wt%, especially 1-70 wt%, of the active ingredient contain. The weight ratios of TPN and the phenylamide compound of formula I will preferably be between 1: 3 and 1:13, more particularly in the range from 1: 4 to 1:12, especially in the range from 1: 4 to 1: 11, for example 20 from 1: 5 to 1:11. Although the amount of surfactant to be used is not critical, recommended compositions will contain 1-10% (w / w) especially 2-5% (w / w) surfactant. Examples of suitable surfactants are any commercially acceptable surfactant suitable for use in a liquid formulation such as Nonypole 100 and Demole Nf

Except the active ingredients, surfactant. agent (s) and diluent (water), the composition may contain other ingredients such as, for example, thickeners acceptable in the agricultural field.

Typical examples of such preparations contain, for example, 0.1-1 wt% thickener.

While it is not necessary to limit the sprayed amount of the chemical material, it is usually convenient to do this approximately in an amount of 1-500 g per 10 ares (hereinafter referred to as "a") as the active ingredient (AB) for its spray application over a field where crops grow and use approximately 0.1-5.0 kg (AB5 / 10a in case of 8900641.Γ * -4 application in soil).

There are, of course, general standards to be set if necessary depending on the varieties of the crops, the types of diseases and the degree of damage, the season period, the weather, the forms of the chemical preparation and so on.

Hereinafter, the reference preparations and forms of the obtained preparations as embodiments of the preparation proposed according to the present invention are described, the forms of such preparations being of course not limited to them.

10

Example 1.

A concentrated Metalaxyl slurry of the following composition was prepared by mixing followed by grinding with a wet type grinder (Eigner motormill from Eiger 15 Engineering Limited.), To obtain a particle size of 1.5 µm in VMD, controlling the total meal;

Metalaxyl 25 parts

Nonypole 100 1 part (supplied by Sanyo Kasei

Kcgyo Co. Lt.) 20 Demole N 2 parts (Provided by Kao Co. Ltd.)

Water 72 parts.

Example 2.

A concentrated oxadixyl suspension of the following composition was also prepared analogously to the method described above (particle size is 1.5 µm in VMD):

Oxadixyl 25 parts

Nonypoly 100 1 part

Demole N 2 parts 30 Water 72 parts

Examples 3-6 (reference example).

A concentrated TPN suspension was prepared by uniformly mixing and comminuting the following ingredients with a wet-type grinder to obtain particles of varying sizes in VMD controlling the total meal: 89 0064 1 t - 5- TPN 50 parts

Nonypole 100 1.5 part

Share Demole N 3

Water 45.5 parts 5

In the reference examples 3-6, the particle sizes in VMD were as follows:

Example 3 0.5 p

Example 4 1.0 μι. Example 5 1.5 μιη

Example 6 5.0 μιη

Example 7.

TPN with a concentrated Oxadixyl suspension of the following composition was prepared by the same method as used in Example 1 (the particle size is 1.0 µm in VMD): TPN 32.9 parts

Oxadixyl 6.4 parts

Nonypole 100 1.5 parts 20 Demole N 3 parts

Water 57.1 parts

Example 8.

TPN with a concentrated Methalaxyl suspension of the following composition was prepared according to the same method as in Example 1 (particle size is 1.5 μι in VMD): TPN 20 parts

Methalaxyl 2 parts

Nonypoly 100 1 part 30 Demole N 2 parts

Water 75 parts

Example 9.

TPN with a concentrated Oxadixyl suspension of the following composition was prepared by the same method as used in Example 1 (particle size is 0.5 µm in VMD): TPN 42 parts

Oxadixyl 6 parts 8900641.

-6-

Nonypole 100 1.5 parts

Share Demole N 3

Water 47.5 parts 5 (3) Effect of the invention.

The composition of this invention is effective in combating a wide variety of diseases from many agricultural and horticultural crops. Examples of such diseases are:

Rice: Pyricularia oryzae, Cochliobolus miyabeanue, Rhizoctonia solani, Gibberella fujikuroi, Rhizopus sp,

Wheat: Puccinia recondite f.sp. tritici, Puccinia itriiformis, Ustüago is tritici, Beptoria tritici, Cochliobolue sativus, Erysiphe graminis f. sp, tritici, Typhula incarnate

Potato: Phytophthora infestans, Alternaria solani, Rhizoctonia solani soybean: Feronosporamanshurica, Cercospora eojina, Septoria glycines, 20 Sclerotinia sclerotiorum, Fhakopsora pachyrhizi, Cercospora kikuchii

Adzuki Cercospora canescens, Uromvces azukicola, Mycosphaerella bean: cruenta, Erysiphe pisi ^ Groundnut: Mycosphaerella araehidis, Mycogphaerella berkeleyi,

Sclerotinia araehidis

Tobacco: Alternaria longipes, Phytophthora nicotianae var, nicotianae,

Sclerotinia sclsrotiorum, Rhizoctonia solani, Pythlum debaryanum, Cercospora nicotianae, Erysiphe cichoracearum 30

Sugar Peronospora schachtii, Cercospora beticola, Rhizoctonia solani beet:

Tomato: Botrytis cinerea, Cladosporium fulvum, Phytophthora infestans, Sclerotinia sclerotiorum, Alternaria solani, 35 Cercospora fuligena, Fusarium oxysporum f. sp, lycopersici,

Rhizoctonia solani

Eggplant: Botrytis cinerea, Verticillium dahliae, Phytophthora capsici, Corynespora melongenae, Sphaeratheca fuliginea, 89 0 0 6 41: - ^ ycove ^ 03 ^ a nattrassii% -7-

Kalabas- Fseudoperonospora cubcnsls, Phytophthora capsici, Botrytis-like: cinerea, Sclerotinia sclerotiorum, Cladosporium cucumerinum,

Coletotrichum layersarium, Mycosphaaerella melonis, Fusarium oxysporura f. sp. cucumerinum, Sphaerotheca 5 fuliginea, Rhizoctoniaeolani

Chinese Peronospora brassicae, Cercosporella brassicae, Sclerotinia cage .- $ clerotiorum, Flasmodiophora brassicae 10 onion: Feronospora destructor, Botrytis allii, Phytophthora porri sia: Bremia lactucae, Botrytis cinerea, Cercospora longissima,

Sclerotinia sclerotiorum 15 Strawberry: Botrytis cinerea, Sphaerotheca humuli, Dendrophoma obscurans chrysan- Fuccinia chrysanthemi, Erysiphe ciehoracearum theme: 20 cyclamen: Botrytis cinerea

Rose: Diplocarpon roe & e, Sphaerotheca pannosa

Citrus: Fenicillium fructigenum, Botrytis cinerea, Diaporthe citri, 25 Elsinoe fawcetti

Apple: Oymnospörangium yamadae, Phomopsis mali, Stereum purpureum, Alternaria mali, Venturia inaequalis, Podosphaera leucotricha, Monilinia mali 30

Pear: Gymnosporangium asiatieum, Alternaria kikuchiana,

Venturia nashicola

Peach: Monilina fructicola, Cladosporium carpophilum, Phomopsis 35 sp., Taphrina deformas

Grape: Plaamopara viticola, Botrytis cinerea, Pseudocercospora vitis,

Elsinoe ampelina, Glomerella cingulata, Pestalotia menezesiana, Phakopsora axnpelopsidis, Fhomopsis viticola, 40 Uninulanecator 8900641 · -8-

Thus, the composition of this invention, a "liquid" formulation, makes the following points clear.

Since the preparation is already dispersed in a liquid, it is not very susceptible to cohesion in dilute water 5 and thus it is possible for the chemical compound to maintain the optimized particle size it has.

Since it is not necessary to add a solid material as a diluent, the decomposing action of the solid material may be avoided. As a result of these characteristics, the active ingredients can perform their action with remarkable efficiency, thereby providing an enhanced preventative effect. For its actual application, the excellent dispersion in water makes it possible to mix well with water, so that it is easy to formulate its solution before spraying. Since the formulation also has excellent suspending properties, the chemical solution can maintain a uniform suspension state for a long time after its formulation, allowing the solution to be in a predetermined concentration for the duration of from the beginning from spraying to finishing spraying, nor will spraying be hindered by clogging the sprayer with the chemical. After the wettable powder preparation is sprayed, some stains (traces of the sprayed solution) remain on the fruits and leaves, but the preparation according to this invention makes it possible to harvest products with an extremely small amount of stains, as it does not contain a mineral constituent that causes these stains. In addition, this preparation, which is not powdery, allows for a safer application.

Typical assay methods and results are described below to specifically explain the effect of the composition of this invention.

However, these are only examples and the uses of this invention are of course not limited to them.

89 006 41 -9-

Examine example 1.

A sample solution diluted to a predetermined concentration (20, 10, 5, 2, 1 and 0.5 ppm am) was sprayed evenly on the leaves of tomatoes (Redcherry variety) at the true leaf stage, in an amount of of 200 1/10 a, which were dried in a greenhouse for 2 hours. After air-drying, zoospores of Phytophthora infestans were inoculated onto the leaves by spraying. The incubation was carried out at a temperature of 21 ° C and a relative humidity of 100% for two days. Five days after inoculation, the infected areas of the 3, 4 and 5 leaf stage were assessed and the intensity of the disease was determined. Disease control was determined by the following formula: intensity of the disease treated 15 (1- ----------------------------- ------------) x 100 intensity of the untreated disease and the EC 90 values were calculated.

The results of Study Example 1 are shown in Table 1 - Table 7.

20

Examine example 2.

A sample solution diluted to a predetermined concentration (20, 10, 5, 2, 1 and 0.5 ppm am) was sprayed evenly onto the leaves of cucumbers (Tokiwahikari 3gou Pgata variety) at the true 2 leaf stage with a 200 1/10 a, which were dried in a greenhouse for 2 hours. By air, zoosporangia of Pseudoperonospora cubensis were inoculated on the leaves. The incubation was carried out for two days at a temperature of 21 ° C and a relative humidity of 100%. five days after inoculation, the infected areas of the 1 and 2 leaf stage were assessed and the intensity of the disease was determined. The control of the disease was determined by the expression: intensity of the treated disease 35 (1- ------------------------------ --------) x 100 intensity of the untreated disease and the EC 90 values were calculated.

The results of Study Example 2 are shown 83 00 641. "-10- in Table 1 and Table 8 - Table 13.

Examine example 3.

According to the same test method as test for picture 1, a sample solution was sprayed evenly on the leaves of tomatoes, which were dried in a greenhouse for 24 hours. After air drying, the tested plants were treated with an artificial rain load of 40 ml for 1 hour. 3 hours after the moderate rain load Zoospores of Phytophthora infestans were inoculated on the leaves. Incubation and evaluation were performed as described above.

The results of Study Example 3 are shown in Table 14 - Table 20.

15 X + Y

EC90 (th) = ——--------------

x Y

EC (a) 90 EC (b) 90 SF = EC90 (th) / EC90 (ob) 20 8900041? -11-

Table 1. Fungicidal activity (EC90) against Phytophtora infestans and downy mildew (Pseudoperonospora cubensis).

EC90 (ppm a.m.)

Particles- Phytophthora False

No. size I infestans mildew

Formulation (ym) 1 Metalaxyl 25w / w% FL 1.5 3.8 3.3 2 Oxadixyl 25w / w% FL 1.5 11.4 10.7 3 Chlorothalonil 50w / w% FL 0.5 19.9 17 .4 4 Chlorothalonil 50w / w% FL 1.0 8.4 8.9 5 Chlorothalonil 50w / w% FL 1.5 9.9 10.2 6 Chlorothalonil 50w / w% FL 5.0 '17.2 17. 1 7 Oxadixyl 6.4w / w% FL 1.0 2.8 2.9

Chlorothalonil 32.0w / w% FL

8 Chlorothalonil 75w / w% HP 20.5 21.3 890 06 41 -12-

Table 2. Theoretical EC90 for different mixtures of TPN and Metalaxyl against Phytophtora infestans in tomatoes.

(ppm a.m.)

Fungicide TPN FL

----- TPN WP

n. 0.5 μιη 1.0 pm 1.5 pm 5.0 pm

Ratio 1: 1 6.4 5.2 5 ^ 5 6/2 -

2 8 ^ 3 6 / Γ_ 6 ^ 5 7 ^ 9 I

3 9.7 6.5 7 /) 9 / L 9.8

4 10.8 6.8 7 ^ 5 ϊζϊ I

5 ϊϊ / 7 7 /) 7.8 10.8 I.

6 12.4 ϊβ- 8 / ΐζί -

7 13/7 / ~ 8/3 Ιϊ /) I

8 13.5 7.4 8 ^ 4 ϊξϊ - 9 14 /) 7 / 8/5 12/7 -

ÏÖ 14 ~ 4 7/3 8β 'Ï3 ~ Ö I

- - _ - —_ -

12 15 /) 7/7 8 / 13/5 I

13 15 / 7/7 8 / 13.7 I

Ϊ4 ~ "15/5 7β 8 /) 13/5 ~ 15 15/7 7 / 9/5 ϊζϊ 890 0641." -13- f t

Table 3. Fungicidal activity of different mixtures of TPN and

Metalaxyl against Phytophthora infestans in tomatoes (observed EC90).

(ppm a.m.) N. Fungicides

XT TPN FL

\ ---- TPNWP

n. 0.5 pm 1.0 pm 1.5 pm 5.0 pm

Ratio J

1: 1 3 ~ 6 2 ^ 9 3 /) 3/5 I

2 4/5 2 / i 3 ^ L 4.0 I

3 4 ^ 9 2 ~ 5 2/7 4 ^ 3 ζϊ

4 5/3 2/3 2 / Γ 4/5 I

5 5/7 2/3 2 /} 4/5 I

6 5/9 2/3 3/3 4/3 I

7 5/3 2 ~ 5 3/3 4/9 I

8 6 / L 2 ^ 5 3 /) 5; 0 I

9 6 ~ 4 2/3 3/3 5 / L I

ÏÖ 6/3 2/7 3/2 5/3 -

ÏÏ 6 / Γ 2/7 5/7 I

Ï2 7/2 2/2 3/2 5/9 -

13 7/2 2 / y 3/2 6y4 I

14 7/9 3 ^ 3 ~~ ÏÏ 6 / Γ "is y'y ~ y y ~ 8300641 /

Table 4. Synergy factor (SF) for different mixtures of TPN

and Metalaxyl against Phytophthora infestans in tomatoes.

-14-

xFungicides TPN FL

N. ---- TPN WP

n. 0.5 µm 1.0 µm 1.5 µm 5.0 µm

Ratios \ _________ 1: 1 1.8 1.8 1.8 1.7 2 1.8 2.1 2 ~ ï 2/3 - 3 2/3 2/5 2/5 2 / Γ ζθ

4 2 /) 2/7 2/7 2/3 I

5 2/3 2/3 2/7 2 / I

6 2 / 2/3 2/7 2 ~ 4 I

^ ^ ^ 2 ^ 8 2 ~ 4 I

8 2/3 3/3 2/3 2/5 -

9 2/2 2 /) 2/3 2/5 I

2/3 2/7 2/3 I

Π ζϊ 2/3 2/7 2/3 - 12 2 / Γ "2.8 2.8 2.3

13 2 / L 2/3 2/7 V I

14 2 / Γ 2 / Γ 2.2 2.0 15 ΐ / 3 ζθ 2 /) Γ / 3 - 89 0 0 641.

Table 5. Theoretical EC90 for different mixtures of TPN and

Oxadixyl against Phytophthora infestans in tomatoes.

-15- _____ (ppm a.m.) N. Fungicides

NT TPN FL

---- TPN WP

N. 0.5 µm 1.0 µm 1.5 µm 5.0 µm

Ratio 1: 1 14.5 9.7 10.6 13.7

2 16.0 9.2 10.4 14/7 I

3 16.8 9 /) ÏÖ / 2 15 ^ 3 17 ^ 1 4 17/3 8/3 ÏÖ ^ i 15/5 - 5 17/3 8/3 lÖ ~ JL 15/3 -

6 18 /) 8 ~ / 16 /) I

7 18/3 8 / Γ ~ lfyï 16/3 I

8 18.4 8.7 10.1 16.3

9, 18.5 8/3/16/4 I

ÏÖ '18.6 8 / Γ 10.0 16.4 Π 18/7 8/3 10.0 16.5 ~ Ϊ2 18.8 8.6 10.0 16.6 13 18.9 8 / Γ 10, 0 16.6 14 19 /) 8 / Γ "10.0 16.6 ~ 15 19 /) 8 / Γ 10.0 16.7 8900641 Γ -16-

Table 6. Fungicidal activity for different mixtures of TPN and

Oxadixyl against Phytophthora infestans in tomatoes (observed EC90).

ς -------- t & pm a.lïlj_

Xungicides TPN FL

\ v TPN WP

\ 0.5 μι 1.0 μιη 1.5 μm 5.0 μm

Ratios ^ _ I j τμ:

2 6.7 3.6 4 ^ 3 J 7 ^ 1 I

3 6.9 3.2 3.6 6/3 12.8

4 6 ^ 8 2 ^ 9 3 ^ 4 6 ^ 5 I

5 6.9 2.8 3.3 6 ^ 6 I

6 7/3 2/7 3/3 ~ 6/5 I

7 6/3 2/5 3 ^ 2 6 ^ - 8 6 ^ 9 2 ~ 6 3 ^ 2 6/5 ~

9 6/9 2 ~ 6 3/2 6/5 I

ÏÖ 7/5 2/3 3/2 6/3 I

ïï 7 /) 2/3 3/2 6 ~ 8 - 12 V 2JT 3.2 6.8 -

13 yT 2 ^ 8 3 / Γ 7/5 I

~ 14 7/5 M 3/7 7/6 I.

15 8.1 3.8 4.0 8.0 8 9 0 0 G 4 1

Table 7. Synergy factor (SF) for different mixtures of TPN and

Oxadixy1 against Phytophthora infestans in tomatoes.

-17-

Ns \ Fungicides TPN FL

N. TPN WP

n. 0.5 µl 1.0 µm 1.5 µm 5.0 µm

Ratios \ ______ 1: 1 2.2 2.2 2.0 1.9

2 2.4 2.6 2.4 2 ^ I

3 2 / Γ 2.8 2.8 2/3 ï / 3 4 2/5 3 / L 3 /) 2 ~ T "

5 2/3 3/3 / L 2 ~ 4 I

6 2/5 3.1 2.4 7 2/7 3 ~ 4 ~ 3/2 ~ 2/5 "- 8 2/7 3 ~ 4 3 ~ 2 2 ~ 5 - 9 2/7 3/3 3 / L 2 / Γ ÏÖ 2/7 3/3 3yL ~ 2 ~ i ~ ïï 2/7 3/3 3 ~ / T 2.4 12 2/7 ~ 3 ^ 2 yT 2.4

13 2fi 3 / Γ 3 / L 2 ^ 4 I I

14 yi 2 / S 2 / Γ 2.2 15 2 / Γ 2.2 2.5 2.1 09 006 41 7

Table 8. Theoretical EC90 for different mixtures of TPN and

Metalaxyl against powdery mildew in cucumbers.

-18- f ..

__________ (ppm a .m.) _> Fungicides

X. TPN FL

1 TPN WP

n. 0.5 μπι 1.0 μιη 1.5 μιη 5.0 μπι

Verho-UdingenN ._____ 1: 1 5.6 4.8 5.0 5.5

2 7 / 5/7 6 / ϊμ I

3 8.4 6.3 6/7 8/9 /

4 9/6/7/9 ~ 3 I

5 10.2 6/7 / ÏÖ ^ Ï -

6 ÏÖ / 7/7 / ÏÖ / 7 I

7 ïï / 3 7/8 / * Π / I

8 Ίϊ / 7/8 / ϊϊ / 7: - 9 12/7/8 ~ 4 12 / ~

12/7/7/8/12 / I

Π 12/7 / 8/7 12/7 I

12 13/7 / ~~ 8/12 / I

13 13/7/8/13 / I

14 13/8 / ~ 9/13 / - 15 i 13/7 8/9/13/89 0 0 £ 4 1.

Table 9. Fungicidal activity for various mixtures of TPN and j-taltalyl against powdery mildew in cucumbers (observed EC90).

-19- ___ (ppm'a.m.)

Fungicides TPN FL

N. TPN WP

n. 0.5 μπι 1.0 μπι 1.5 μπι 5.0 μπι

Relationships\___

1: 1 '2.9 2 / Γ ~ 2 ^ 4 2 ^ 8 I

2 3/3 2/3 2/7 3/3 I

3 3/3 2/3 3 / ï 8/7

4 4 / Γ 2 ^ 2 2/3 3/3 I

5 4 ~ 4 2/3 2/5 4JL I

6 4.7 2.4 2.7 4.4

7: 4fi ~ 2.4 2 ~ 8 4/5 I.

8 5fl 2 ^ 4 2 / Γ 4/7 I

: 9 5 ^ 2 ^ 5 4 / ï - ~

ö 5.4 2/5 2/3 5 ^ 1 I.

Π 5/3 2/3 2/3 5 / f ~ 12 5/5 2 / Γ "3.0 5.3 13 5 ~ 6 ~ 2.9 3.2 5.5 14 6/3 3/5 4 / L 6 / Γ - 15 6/5 4 / Γ 4.3 674 - 8900641

Table 10. Synergy factor (SF) for different mixtures of TPN and

Metalaxyl against powdery mildew in cucumber.

-20-

^ 'XFungicides TPN FL

---- TPN WP

n. 0.5 µl lt0 pm 1.5 pm 5.0 pm

Ratio K_________

1: 1 Ï / T | 2 / Γ 2.1 2.0 I.

2 2.2 2r5 ~ 2/2 2 ^ 2 I

3 2.2 2.6 2 ^ 4 2/3 1 ~ Q

4 2J ”3/3 ζδ 2/5 I

5 2/3 3/3 2/3 2/5 I

6 2.3 3/3 2 / y 2 ^ 4 I

7 24 3/3 2/3 2/5 I

8 2 ~ 4 3 / L 3/3 2/5 I.

9 2 / Γ 3.0 2 / S 2/5 ~ I

- - - - -:

U 2/3 3 /) 3/3 2 ^ 4 I

12 ^ 3 3 /) 3 /) I

13 2/5 2/7 2 / Γ 2.4 I

14 2 / L 2/3 2/2 2/3 I

15 2 / l 2/3 ~~ 2.1 2.1 - 8900641.

Table 11. Theoretical EC90 for different mixtures of TPN and

Oxadixyl against powdery mildew in cucumber.

-21- _____ (ppm a.m.)

N ^ ungicides TPN FL

N. ---; - TPN WP

Nv 0.5 μι 1.0 μπι 1.5 μπι 5.0 μπι

Ratios X__________ 1: 1 13.3 9.7 10.4 13.2

2 9ί 9 ^ 4 ~ 10 .4 14 ~ 3 I

3 ΪΙ /> 9/3 10 ^ 3 14 ~ 9 17 ^ 1 4 15 ^ 5 9/2 10 ^ 3 15/3 -

5 15 / ϊ 9/2 ÏÖ / 3 15 ^ 6 I

6 16 ^ 0 ~ Εμ ΐθ ~ 3 15/3 I

7 Ϊ6μ 9 / L 10 ^ 3 15 /) I

8 16.3 9 ^ 1/3 16 /) I

9 16 ^ 4 ~ 9μ 10.3 Ϊ6 ~ Ϊ -

ÏQ 16.5 9 ~ 0 ÏÖ / Ï 16/2 I

ϊϊ 16 / ϊ 9 /) ÏÖ / 2 16.3 I

12 16/5 9 /) ÖÖ / 2 ϊ ^ 4 I

13 16/7 9 /) 10.2 16.4 14 16.7 9 /) 10.2 16.4 15 16.7 δδ 10.2 16.5 - 8900641; -22-

Table 12. Fungicidal activity for various mixtures of TPN and Oxadixyl against downy mildew in cucumber (observed EC90).

(ppm a. m.)

\ ungicides · TPN

\. ---- TPN WP

0.5 µl 1.0 µm 1.5 µl 5.0 µl

Ratios \ __________ 1: 1 6.4 4.7 5.0 6.1

2 6.6 4.0 4 ^ 6 6 ^ 1 I

3 6.6 3; 5 4; 0 6 ^ 2 ϊίζο ~ 4 6.3 3.0 3 ^ 4 64 ~

5 6.4 2.9 3; 4 6 ^ 2 I

6 6.5 2.9 3.4 6/3 I

7 6.4 2.8 3.3 6.2

8 6.4. 2.8 3/3 6/2 I.

9 6 ^ 4 2/8 3/3 6/3 I

6/0 6/3 ~ 2 ^ 8 3 ^ 4 '6/4 I ~

2/ 64 2/3 3 ^ 4 64 I

12 6/7 24 3 ~ 4 ~ 64 I

- - - - - -

- - - - - I

15 74 3 / Γ 4.6 745 - 89 0 06 A1?

Table 13. Synergy factor (SF) for different mixtures of TPN and

Qxadixyl against downy mildew in cucumber.

a

-23- ________________________ (ppm a.m.)

S \ vFungic iden i TPN FL

N. TPN TO

0.5 µm 1.0 µm 1.5 µm 5.0 µm

Ratios X_____ 1: 1 2.1 2.1 2; 1 2.2

2 2 ^ 2 2 ^ 4 ~ "2 / Γ ~ 2/3 I

3 2 ^ 3 2/7 2 / Γ] 2 ^ 4 ï ^ ï 4 2 ^ 5 3 / L 3 / Γ 2r5.

5 ”2 / F ~ 3.2 3.0 '2/5 I.

6 2.5 3.1 3.0 2.5 7 2/5 3/3 3 ^ 1 y 2/5 - 8 2.5 3/3 3 / ï ^ 2.6 - 9 2/3 3 ~ 3 3 ^ Γ 2.6 ÏÖ 2/3 3 ^ 2 3 ^ 0 ”2.5 Π 2 ~ 5 3/2 3 / Γ 2r5

12 2/5 3 3 /> 2 / F ~ ~ I

13 2.5 3.1 3.0 2.5 14 2/3 3 /) 2 / Γ 2.3 Ï5 ~ 2.1 2.6 2.2 2.2 89 00 641.

-24-

Table 14. Fungicidal activity (EC90) after an artificial rain load against Phytophtora infestans.

__ (ppm a.m.)

Particles- Phytophthora 1Ί "θ · arootte

Formulation y. , infestans _ (μΐή) 1 Metalaxyl 25w / w9rFL 1.5 3.8 2 Oxadixyl 25w / w% FL lf5 12; 2 3 Chlorothalonil 50w / w% FL 0.5 49.8 4 Chlorothalonil 50w / w% FL 1, 0 19.3 5 Chlorothalonil 50w / w% FL 1.5 23.4 6 Chlorothalonil 50w / w% FL 5.0 51.6 7 Oxadixyl 6.4w / w% FL 1.0 5.3

Chlorothalonil 32.0w / w% FL

8 Chlorothalonil 75w% WP 55.0 8900641.

Λ

Table 15. Theoretical EC90 for different mixtures of TPN and

Metalaxyl against Phytophthora infestans in tomatoes.

-25- __ (ppm a.m.)

N ^ ungicides 1

N. ---- TPNWP

N'v 0.5 pm 1.0 pm 1.5 pm 5.0 pm

Ratios ^ ___._______ 1: 2 10.1 8.3 8.8 10.2

5 16 ^ 8 ^ 6 12/5 17/3 I

9 22.9 13.8 15.6 23 ^ 2 23/3 12 26jï 14/5 16/5 26/5 I '15 28/7 15/5 17 / ï 29 ^ 2 Γ "

Table 16. Fungicidal activity after artificial rain load of various mixtures of TPN and Matalaxyl against Phytophtora infestans in tomatoes (observed EC90) _ | _ (ppm a.m.)

X Fungicides TPN FL

\ --- η --- TPNWP

n. 0.5 µm 1.0 µm 1.5 µm 5.0 µm

Ratios \ _____ 1: 2 5.2 3.3 3.7 5.3 5 7.6 3.8 4.3 7.5 - 9 ÏÖ / 3 4/5 5/2 10/5 22/5

12 12.0 4 / ï 5/3 ïï / 3 I

Ü ϊζΕ 7 ^ 4 8/7 15.1 ~ 8900641.

-26-

Table 17. Synergy factor (SP) after artificial rain load for various mixtures of TPN and Metalaxyl against Phytophthora infestans in tomatoes.

\ TgiCia0n I TPN fl ^

N. i I i TPNWP

N. Οφ μπι 1τ0μχη lf5 μπι 5.0 μ

Proportions ^ _____ ___

ï Π ljT 2.5 2.4 | ΰ) I

5 2.2 3.1 3.0 2.3

9 2 ^ 2 3 ^ 1 3 ^ 0 2 ^ 3 ^ ^ L

12 2 ^ T 3.0 2.9 2.3 * / 9 2> 1__2.1. 1.9 __-

Table 18. Theoretical EC90 for different mixtures of TPN and Oxadixyl against Phytophthora infestans in tomatoes.

(ppm a.m »)

Njkingicides j TPN FL

--- TPNWP

0.5 μπι 1.0 μπι 1.5 μπι 5.0 μπι

RatioN ._______—- 1: 2 24.6 16.2 17.9__24 / 9 __- 5 32/9 17.6 20.3 33.5 - 9 38 ^ 1 18.2 39.0 40.7 12 4YY ~ 18.5 21.9 '41.3 __- Ϊ5 41 ^ Γ 18.6 ~ 22.1 43.9 8900641.

Table 19. Fungicidal activity after: an artificial rain load for various mixtures of TPN and Oxadixyl against Phytophthora infestans in tomatoes (observed EC90}.

-27-

\ yFungicides TPN FL

TPN WP

N. 0 $ pm 1.0 μπι 1.5 μπι 5.0 μπι

Ratios ^ .______ 1: 2 11.6 6.3 7.2 11.9 5 12 ^ 4 5 / Ü 6 ^ 4 13 ^ 3 - 9 14 ^ 2 6 ^ 8 15.6 32 ~ 5

12 ΐζϊ 5y6 6 ~ £ lp I

15 19 / Ö 7.6 9p ~ 18.7 __-

Table 20. Synergy factor (SF) after artificial rain load for various mixtures of TPN and Oxadixyl against Phytophthora infestans in tomatoes. (Ppm a.m.)

XFungicides TPN FL

\ ---- TPN WP

0.5 μι 1.0 μπι 1.5 μπι 5.0 μπι

Ratios \ _________ 1: 2 2.1 2.6 2.5 2.1 5 2.7 3.3 3.2 2f5 __- “9 2/7 3.2__2.5 1.3 12 2.7 3 ^ 3 ~ 3.2__2 ^ 5 __- 15 Ϊ ~ Γ 2.1 2.4 I 2.3 8900641.

The aforementioned test results show that the preparation proposed according to the invention has an excellent fungicidal effect and a great synergistic effect.

-28- 89 00 64 1: “

Claims (9)

A liquid fungicidal composition comprising the active ingredients a) a compound of formula I, wherein R is the methoxymethyl, benzyl, chloromethyl, 2-tetrahydrofuryl or 2-furyl group, 2 the 2-oxo-1, 3-oxazolidin-3-yl, 1- (methoxycarbonyl-methyl, 2-oxo-thiolan-3-yl or tetrahydro-2-oxo-3-furanyl, a hydrogen or chlorine atom, and also a hydrogen- or chlorine atom, and b) contains tetrachloroisophthalonitrile, and an aqueous surfactant, wherein the weight ratio of the compound of formula I to tetrachloro-15 isophthalonitrile is between 1: 2 and 1:15 and wherein the solids have a particle size in the range from 0.5 to 5 microns at the 50% volume accumulation point. 2. Preparation according to claim 1, characterized in that the weight ratio of compound of formula I to tetraisophthalonitrile is between 1: 3 and 1:13, more particularly between 1: 4 and 1:12, especially between 1: 4 and 1:11. Preparation according to claim 1, characterized in that the solid components have a particle size in the range of 0.8-2.5 microns, preferably between 0.8 and 1.8 microns and especially between 0.5 and 25 liters. .5 microns at the 50% volume accumulation point. Preparation according to claim 2, characterized in that the solid components have a particle size of 0.8 to 2.5 microns, preferably 0.8 to 1.8 microns and especially 0.5-1.5 microns, at the 50% volume accumulation point. Preparation according to any one of claims 1 to 4, characterized in that it is a compound of formula I, wherein R is the methoxymethyl, benzyl, chloromethyl, 2-tetrahydrofuryl or 2-furyl group, Z is the 2-oxo 1,3-oxazolidin-3-yl-, 1- (methoxycarbonyl) -ethyl, 2-oxo-thiolan-3-yl or tetrahydro-2-oxo-3-furanyl group, 890 0 6 41. -30- 8 X, represents a hydrogen or chlorine atom and 1 X ^ a hydrogen atom. Preparation according to claim 5, characterized in that it contains a compound of formula I, wherein 5 a) R is methoxymethyl, Z is 1- (methoxycarbonyl) ethyl and X. is hydrogen 1 b) R is methoxymethyl, Z ' 2-oxo-1,3-oxazolidin-3-yl and X is hydrogen 1 c) R is benzyl, Z is 1- (methoxycarbonyl) ethyl and X is 10 hydrogen d) R is chloromethyl, Z is tetrahydro- 2-oxo-3-furanyl and X ^ is hydrogen e) R is 2-furyl, Z is 1- (methoxycarbonyl) ethyl and X ^ is hydrogen 15 or f) R is methoxymethyl, Z is 2-oxo-1,3 oxazolidin-3-yl and X, is chlorine. A composition according to claim 1 containing 1-98% by weight, preferably 1-70% by weight, of active ingredients. 8. Method for preparing or manufacturing a. preparation according to claim 1, characterized in that the components are mixed and the solid particles thereof are comminuted to the desired particle size. 9. Compositions and methods as described in the specification and / or examples. o-o-o-o-o-o-o-o-o X Δ'i 89 0 0 64 1. /