Fungicidal combinations of active substances

Description of the invention

The present invention relates to new combinations of active substances, consisting, on the one hand, of a known fluorobenzothiazole derivative, and, on the other hand, of known active substances, which combinations are very well suited for controlling phytopathogenic fungi. The invention also relates to the use of these combinations for the production of fungicides and a process for the preparation of the fungicides.

Isopropyl 1 - ({[1- (6-fluoro-1,3-benzotriazol-2-yl) ethyl] amino} carbonyl) -2-methylpropylcarbamate is known to have fungicidal properties (cf. Patent Document No. EP-A1-775 696). The effectiveness of this agent is good, however, when used in low doses, it leaves something to be desired in many cases.

It is further known that numerous triazole derivatives, aniline derivatives, dicarboximides and other heterocyclic compounds can be used to control fungi [cf. EP-A Patent Documents No. 0 040 345, DE-A 22 01 063, DE-A 23 24 010; Pesticide Manual, ed. IX, pp. 249 and 827 (1991); Patent documents EP-A 0 382 375 and EP-A 0 515 901]. Also in the case of these compounds, when used in low doses, their activity is not always sufficient.

Finally, it is also known that 1 - [(6-chloro-3-pyridinyl) methyl] -N-nitro-2-imidazolidinimine [cf. Pesticide Manual, 2nd ed. IX, p. 491 (1991)]. However, the fungicidal properties of this agent have not yet been described.

Then it is already known that 1- (3,5-dimethylisoxazole-4-sulfonyl) -2-chloro-6,6-difluoro- [1,3] dioxolo [4,5f] benzimidazole exhibits fungicidal properties (cf. Patent No. WO 97-06171).

It is also already known that substituted azadioxacycloalkenes have fungicidal properties (cf. Patent Document No. EP-B-712 396).

Finally, it is also known that substituted halopyrimidines have fungicidal properties (cf. Patent Documents DE-A1-196 46 407, EP-B-712 396). It has now been found that new combinations of active substances containing at least one compound, a fluorobenzothiazole derivative of the formula:

<img file="PL200668B1_D0001.tif" />

and (1) a traiazole derivative of the formula

<img file="PL200668B1_D0002.tif" />

wherein:

X is chlorine or a phenyl group and Y is

<img file="PL200668B1_D0003.tif" />

or - · CHI

OH

Or (2) a triazole derivative of the formula:

<img file="PL200668B1_D0004.tif" />

or (3) an aniline derivative of the formula:

<img file="PL200668B1_D0005.tif" />

in which: R.¹ is hydrogen or a methyl group or (4) N- [1- (4-chlorophenyl) ethyl] -2,2-dichloro-1-ethyl-3-methylcyclopropanecarboxamide of the formula:

<img file="PL200668B1_D0006.tif" />

or (7) an aniline derivative of the formula:

<img file="PL200668B1_D0007.tif" />

or (10) 8-tert-butyl-2- (N-ethyl-Nn-propylamino) methyl-1,4-dioxaspiro [5.4] decane of the formula:

<img file="PL200668B1_D0008.tif" />

(spiroxamine)

Or (11) a compound of the formula:

<img file="PL200668B1_D0009.tif" />

h₃c^with (trifloxystrobin) or (13) a compound of the formula:

<img file="PL200668B1_D0010.tif" />

or (20) a hydroxyethyl triazole derivative of the formula:

<img file="PL200668B1_D0011.tif" />

or (21) 1 - [(6-chloro-3-pyridinyl) methyl] -N-nitro-2-imidazolidinine of the formula:

<img file="PL200668B1_D0012.tif" />

(imidacloprid) (XXII)

PL 200 668 B1 or (22) an oxazolidinedione having the formula:

<img file="PL200668B1_D0013.tif" />

or (24) a guanidine derivative of the formula:

<img file="PL200668B1_D0014.tif" />

where: m represents integers from 0 to 5 and R.³ represents hydrogen (17 to 23%) or a group of formula ^_c = nh nh₂ (77 to 83%) or (25) a triazole derivative of the formula:

<img file="PL200668B1_D0015.tif" />

(penconazole) or (26) a halobenzimidazole of the formula;

<img file="PL200668B1_D0016.tif" />

or (27) a halopyrimidine of the formula:

<img file="PL200668B1_D0017.tif" />

PL 200 668 B1 or (31) a thiazolecarboxamide of the formula:

<img file="PL200668B1_D0018.tif" />

or (36) a diamide of the formula:

<img file="PL200668B1_D0019.tif" />

or (37) a methoxyacrylate derivative of the formula:

<img file="PL200668B1_D0020.tif" />

or (42) a phosphonic acid of the formula:

H — P — OH

OH (ΧΧΧΧΪΓΙ) (phosphonic acid) or (45) copper compounds:

(a) copper oxychloride (XXXXVIa) or (47) a triazole derivative of formula c):

<img file="PL200668B1_D0021.tif" />

PL 200 668 B1 or d)

<img file="PL200668B1_D0022.tif" />

or e)

<img file="PL200668B1_D0023.tif" />

or f)

<img file="PL200668B1_D0024.tif" />

or (g)

<img file="PL200668B1_D0025.tif" />

or (h)

<img file="PL200668B1_D0026.tif" />

(tetraconazole)

Or (48) a compound of the general formula:

<img file="PL200668B1_D0027.tif" />

wherein:

R¹ represents a phenyl group, a 2-naphthyl group, a 1,2,3,4-tetrahydronaphthyl group or an indanyl group, each optionally optionally substituted with fluorine, chlorine, bromine, methyl or ethyl or (49) N-methyl-2- (methoxyimino) ) -2- [2 - ([1- (3-trifluoromethylphenyl) ethoxy] iminomethyl) phenyl] -acetamide of the formula:

<img file="PL200668B1_D0028.tif" />

or (50) 2,4-dihydro-5-methoxy-2-methyl-4- [2 - ([([1- (3-trifluoromethylphenyl) ethylidene] amino) oxy] methyl) phenyl] -3H-1,2 , 4-triazol-3-one with the formula:

<img file="PL200668B1_D0029.tif" />

or (51) a compound of the formula:

<img file="PL200668B1_D0030.tif" />

show very good fungicidal properties.

The following active ingredients are preferred as mixing partners with the compounds of formula (I):

(3) tolylfluanid (IVb), (7) fenhexamid (VIII), (11) azoxystrobin (XII),

(12) trifloxystrobin (XIII), (13) a compound of formula (XIV), (20) a compound of formula (XXI), (27) a compound of formula (XXVIII) and (45) copper compounds:

(a) copper oxychloride (XXXXVIa).

Preferably, in the active ingredient combinations, the weight ratio of active ingredient of formula (I) to active ingredient is:

- groups (1) are in the range from 1: 0.1 to 1:50,

- groups (2) are in the range from 1: 0.1 to 1:50,

- groups (3) are in the range from 1: 1 to 1: 150,

- groups (4) are in the range from 1: 0.1 to 1:10,

- groups (7) are in the range from 1: 0.1 to 1:50,

- groups (10) are in the range from 1: 0.01 to 1:50,

- groups (11) are in the range from 1: 0.1 to 1:50,

- groups (12) are in the range from 1: 0.1 to 1:50,

- groups (13) are in the range from 1: 0.1 to 1:50,

- groups (20) are in the range from 1: 0.02 to 1:50,

- groups (21) are in the range from 1: 0.05 to 1:20,

- groups (22) are in the range from 1: 0.1 to 1:50,

- groups (24) are in the range from 1: 0.1 to 1: 150,

- groups (25) are in the range from 1: 0.1 to 1:50,

- groups (26) are in the range from 1: 0.1 to 1:50,

- groups (27) are in the range from 1: 0.1 to 1:50,

- groups (31) are in the range from 1: 0.1 to 1:50,

- groups (36) are in the range from 1: 1 to 1: 150,

- groups (37) are in the range from 1: 0.1 to 1:50,

- groups (42) are in the range from 1: 1 to 1: 150,

- groups (45a) are in the range from 1: 1 to 1: 150,

- groups (47c) is in the range from 1: 0.1 to 1:50,

- groups (47d) is in the range from 1: 0.1 to 1:50,

- groups (47e) is in the range from 1: 0.1 to 1:50,

- groups (47f) is in the range from 1: 0.1 to 1:50,

- groups (47g) are in the range from 1: 0.1 to 1:50,

- groups (47h) are in the range from 1: 0.1 to 1:50,

- groups (48) are in the range from 1: 0.1 to 1:50,

- groups (49) are in the range from 1: 0.1 to 1:50,

- groups (50) are in the range from 1: 0.1 to 1:50,

- groups (51) are in the range from 1: 0.1 to 1:50.

A further object of the invention is the use of the active ingredient combinations as defined above for the production of fungicides.

The invention also relates to a process for the preparation of fungicides, characterized in that the combinations of the active substances defined above are mixed with diluents and / or surfactants.

It has surprisingly been found that the fungicidal effect of the active substance combinations according to the invention is significantly greater than the sum of the effects of the individual active substances.

Thus, there is an unforeseeable real synergistic effect and not just a complement to the action.

From the structure of the active substance of formula (I) it becomes apparent that this compound has two asymmetrically substituted carbon atoms. Therefore, the compound can exist as a mixture of different isomers as well as single isomers.

Preferred compounds of formula (I) are those compounds in which the amino acid portion is isopropyloxycarbonyl-L-valine and the fluorobenzothiazoleethylamine portion is racemic, especially when they have the (R) configuration.

PL 200 668 B1

Formula (II) includes the following compounds:

-1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) butan-2-one with the formula:

<img file="PL200668B1_D0031.tif" />

-1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) butan-2-ol of formula:

<img file="PL200668B1_D0032.tif" />

and -1- (4-phenylphenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) butan-2-ol of the formula:

<img file="PL200668B1_D0033.tif" />

Formula (IV) includes within its scope the aniline derivatives of the formula:

s — cci₂f SO_rN (CH₃)₂ (IVa) (dichlofluanid) and

<img file="PL200668B1_D0034.tif" />

From the formula of the structure of the active substance of formula (V) it becomes apparent that this compound has three asymmetrically substituted carbon atoms. Therefore, this compound can exist as a mixture of different isomers as well as single components.

PL 200 668 B1

The following compounds are particularly preferred:

- N- (R) - [1- (4-chlorophenyl) ethyl] - (1S) -2,2-dichloro-1-ethyl-3t-methyl-1R-cyclopropanecarboxamide of formula:

<img file="PL200668B1_D0035.tif" />

and

- N- (R) - [1- (4-chlorophenyl) ethyl] - (1R) -2,2-dichloro-1-ethyl-3t-methyl-1R-cyclopropanecarboxamide of formula:

<img file="PL200668B1_D0036.tif" />

The hydroxyethyl triazole derivative of formula (XXI) may exist in the "thione" form with the formula:

<img file="PL200668B1_D0037.tif" />

or in the tautomeric form "mercapto" of the formula:

<img file="PL200668B1_D0038.tif" />

(XXIb)

For the sake of simplicity, only the form "tiono" will be quoted each time.

The guanidine derivative of formula (XXV) is a mixture of substances with the common name guazatine. It can be seen from the structural formula of the active substances of formula (XXXXIX) that said compounds can exist as E or Z isomers. Therefore, the product can be a mixture of different isomers, but can also exist as a single isomer. Preferred compounds of formula (XXXXIX) are E isomers.

PL 200 668 Β1

The following compounds are particularly preferred:

<img file="PL200668B1_D0039.tif" />

Oh₃ (XXXXIXa) and

<img file="PL200668B1_D0040.tif" />

and

<img file="PL200668B1_D0041.tif" />

and

<img file="PL200668B1_D0042.tif" />

and

<img file="PL200668B1_D0043.tif" />

Oh₃ (χχχχιχβ) and

<img file="PL200668B1_D0044.tif" />

OH, (XXXXłXf) and their isomers.

PL 200 668 B1

The following active ingredients are also preferred as mixing partners with the compounds of formula (I):

(8) iprovalicarb (VIII) or (26) a compound of formula (XXVII).

The ingredients of the active ingredient composition according to the invention, in addition to the halobenzimidazole of formula (XXVII), are also known.

In particular, the active substances are described in the following publications and patent documents:

(1) compounds of formula (II):

DE-A 22 01 063

DE-A 23 24 010 (2) compounds of formula (III)

EP-A 0 040 345 (3) compounds of formula (IV)

Pesticide Manual, ed. IX, pp. 249 and 827 (1991) (4) compounds of formula (V) and their individual isomers EP-A 0 341 475 (7) compound of formula (VIII)

EP-A 0 339 418 (11) compound of formula (XII)

EP-A 0 382 375 (12) compound of formula (XIII)

EP-A-460 575 (13) compound of formula (XIV)

DE-A 196 02 095 (20) compound of formula (XXI)

WO 96-16048 (21) a compound of formula (XXII)

Pesticide Manual, ed. IX, p. 491 (1991) (22) Compound of formula (XXIII)

EP-A 0 393 911 (24) a compound of formula (XXV)

Pesticide Manual, ed. IX, p. 461 (1991) (25) Compound of formula (XXVI)

Pesticide Manual, ed. IX, p. 654 (1991) (26) Compound of formula (XXVII)

WO 97-06171 (27) a compound of formula (XXVIII)

DE-A1-196 46 407

EP-B-0 712 396 (31) compound of formula (XXXII)

EP-A-0 639 547 (36) compound of formula (XXXVII)

US 1,972,961 (37) compound of formula (XXXVIII)

EP-A-326 330 (42) compound of formula (XXXXIII) known and commercially available (45) a) compound of formula (XXXXVIa) known and commercially available (47) c) compound of formula (XXXXVIIIc)

DE-A-3 406 993

d) a compound of formula (XXXXVIIId) EP-A-68 813

e) a compound of formula (XXXXVIIIe) DE-A-2551560

f) a compound of formula (XXXXVIIIf) EP-A-145 294

g) a compound of formula (XXXXVIIIg) DE-A-3 721 786

h) a compound of formula (XXXXVIIIh) EP-A-234 242

PL 200 668 B1 (48) compound of formula (XXXXIX)

WO 96/23763 (49) a compound of formula (XXXXX)

EP-A-596 254 (50) compound of formula (XXXXXI)

WO 98/23155 (51) a compound of formula (XXXXXII)

EP-A-569 384

The active ingredient combinations according to the invention contain, in addition to the active ingredient of the formula (I), also at least one active ingredient from the compounds of the abovementioned groups (1) to (51). They may also contain further fungicidal active ingredients added to the mixture. The synergistic effect is especially pronounced when the active substances contained in the active compound combinations according to the invention are present in certain weight ratios to one another. However, the relative weight ratios of the active ingredients present in the active ingredient combinations can be varied within relatively wide ranges. In general, 1 part by weight of active substance of formula (I) consists of:

- from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight of an active substance from a cluster (¹)^,

- from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of an active substance from the group (2),

- from 1 to 150 parts by weight, preferably from 1 to 100 parts by weight, of active ingredient according to^rups (³),

- from 0.1 to 10 parts by weight, preferably from 0.2 to 5 parts by weight, of an active substance from the group (4),

- from 0.1 to 50 parts by weight, preferably from 1 to 20 parts by weight, of active substance according to^rups (Λ

- from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of an active substance from the group (10),

- from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight of an active substance from the group (¹¹)^,

- from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight of an active substance from the group (¹²)^,

- from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight of an active substance from the group (¹³)^,

- from 0.02 to 50 parts by weight, preferably from 0.2 to 10 parts by weight, of an active substance from the group (20),

- from 0.5 to 20 parts by weight, preferably from 0.1 to 10 parts by weight of an active substance from the group (²¹)

- from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight of an active substance from the group (²²)

- from 0.01 to 150 parts by weight, preferably from 1 to 100 parts by weight, of an active substance from the group (24),

- from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight of an active substance from the group (²⁵)

- from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight of an active substance from the group (²⁶)

- from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight of an active substance from the group (27)

- from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight of an active substance from the group (³¹)^,

- from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight of an active substance from the group (³⁶)

- from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight of an active substance from the group (³⁷)^,

- from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight of an active substance from the group (⁴²)

PL 200 668 B1

- from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight, of an active substance from the group (45a),

- from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of an active substance from the group (47c),

- from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of an active substance from the group (47d),

- from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of an active substance from the group (47e),

- from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight of an active substance from the group (⁴⁷)

- from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight of an active substance from the group (⁴⁷^)

- from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of an active substance from the group (47h),

- from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight of an active substance from the group (⁴⁸)

- from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight of an active substance from the group (-49)

- from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight of an active substance from the group (⁵⁰)

- from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight of an active substance from the group (⁵¹).

The active substance combinations according to the invention are distinguished by very good fungicidal properties and are suitable for controlling phytopathogenic fungi such as Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes etc. The active substance combinations according to the invention are particularly suitable for controlling Phytophthora. infestans and Plasmopara viticola.

The good plant tolerance shown when the combination of active substances (for combating plant diseases) is used in the required concentrations enables the effects on the above-ground parts of plants, on the plant material and seeds, and on the soil. The active compound combinations according to the invention can be used for foliar application or as dressing agents. The active compound combinations according to the invention are also suitable for use in increasing the harvest yield. They are also moderately toxic and the plant tolerance is good for them.

According to the invention, all plants and parts of plants can be treated with the compounds in question. The term "plants" as used herein includes all plants and plant populations, such as desired and undesirable wild plants and crops (including naturally occurring crops). Crop plants can be plant varieties obtained by conventional breeding and optimization methods, or obtained by biotechnological and genetic engineering methods, or by a combination of these methods and methods, including transgenic plants and plant varieties that, if appropriate, may be protected by plant patents and plant variety laws. The term "plant parts" as used herein refers to any parts and organs of a plant above and below the soil surface, such as shoot, leaf, flower and root, for example leaves, needles, stems, trunks, flowers, fruiting bodies, fruits and seeds, as well as roots, tubers and rhizomes. The term "parts of plants" also includes harvested material and propagation material such as, for example, cuttings, tubers, rhizomes, layering and seeds.

According to the invention, the plants and plant parts are treated by applying the active substances either directly to the plants or plant parts or to their surroundings, living space or inside the warehouse, for example by dipping, spraying, dusting, fogging, lubricating. and in the case of propagation material, especially in the case of seeds, also by coating with one or more layers.

The active substances can be formulated as usual, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, microcapsule preparations made with polymeric materials and seed coatings, and ULV preparations (for low-volume spraying). These preparations are prepared by known methods, for example by mixing the active substances or combinations of the active substances with diluting agents16

These include liquid solvents, pressurized liquefied gases and / or solid carriers, optionally with the use of surfactants, and also emulsifiers and / or dispersants and / or foaming agents.

In the case of using water as an extender, organic solvents can also be used as auxiliary solvents. The following are generally considered as liquid solvents: aromatic hydrocarbons such as xylene, toluene or alkyl naphthalene, chlorinated aromatic hydrocarbons and chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene, or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffinic hydrocarbons, e.g. petroleum fractions, alcohols such as butanol or glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide as well as water.

In the case of liquefied gas diluents or carriers, mention should be made of those liquids which are gaseous at normal temperature and pressure, e.g. aerosol propellants such as butane, propane, nitrogen and carbon dioxide.

Possible solid carriers are, for example: natural mineral flours such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic mineral flours such as highly dispersed silicic acid, aluminum oxide and silicates. The following are considered solid carriers for granules: crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite, as well as synthetic granules obtained from inorganic and organic flours, as well as granules made of organic material such as sawdust , coconut shells, corn cobs, and tobacco stalks.

Suitable emulsifiers and / or foaming agents are, for example: nonionic and anionic emulsifiers, such as polyoxyethylene glycol fatty acid esters, ethoxylated fatty alcohols, for example alkylaryl polyoxyethylene compounds, alkyl sulfonates, alkyl sulfates, aryl sulfonates and also protein hydrolysates . Suitable dispersants are, for example, sulfite lyes and methylcellulose.

The formulation may also include adhesion promoters, such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latex, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids, such as such as cephalin and lecithin, and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, for example iron oxide, titanium oxide, iron blue, and organic dyes such as alizarin, azo and metallophthalocyanine dyes, as well as microelements, for example, iron, manganese, boron salts, can also be used. copper, cobalt, molybdenum and zinc. The preparations contain the active ingredient in an amount generally in the range from 0.1 to 95% by weight, preferably in the range from 0.5 to 90% by weight.

The new active ingredient combinations can be used as such or in the form of formulations as mixtures with known fungicides, bactericides, acaricides, nematicides or insecticides, for example to broaden the spectrum of action or to prevent the development of resistance.

In many cases, a synergistic effect is obtained, which means that the effectiveness of the mixture is greater than that of its individual components.

It is also possible to prepare a mixture with other known active ingredients such as herbicides or with fertilizers and plant growth regulators.

The new active ingredient combinations can be used as such, in the form of the preparations prepared therefrom, or in the formulations obtained therefrom, such as solutions, emulsifiable concentrates, emulsions, suspensions, wettable powders, soluble powders and granules. They are applied in the usual way and consist, for example, in pouring, splashing, spraying liquids, sprinkling, lubricating, dry dressing, wet dressing, dressing with a liquid mortar, dressing in suspension and forming a shell (encrustation).

When the active substance combinations according to the invention are used, the application rates can be varied within a wide range, depending on the method of application.

Thus, in the case of the treatment of plant parts, the doses of the active substance combination are generally in the range from 0.1 to 10,000 g / ha, preferably in the range from 10 to 1000 g / ha.

When applied to seeds, the doses of the active ingredient combination are generally in the range of 0.001 to 50 g / kg of seed, preferably in the range of 0.01 to 10 g / kg of seed.

PL 200 668 B1

In the case of application to the soil, the rates will generally be in the range from 0.1 to 10,000 g / ha, preferably in the range from 1 to 5000 g / ha.

The good fungicidal activity of the active compound combinations according to the invention can be seen from the following examples.

Whilst the individual active substances show some weaknesses in their fungicidal activity, the combinations in question show an activity which exceeds the sum of the actions of the single active substances.

In the case of fungicides, a synergistic effect occurs whenever the fungicidal effect of a combination of active substances is greater than that of the active substances used individually.

The expected effect of a given combination of two active substances can be calculated according to SR Colby ("Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, 15, 20-22 (1967)] as follows.

When:

X =% of the degree of activity with active substance A applied at a dose rate of mg / ha i

Y =% of the degree of activity with active substance B at the dose ng / ha and

E = degree of activity with active substances A and B in doses of min g / ha, then:

X Y 100

The degree of activity is expressed here in%. 0% means a degree of activity corresponding to the degree of activity of the control, while a degree of activity of 100% means that no contamination was observed.

If the actual fungicidal activity is stronger than the calculated damage, then the combination is superadditive in its activity, that is to say it has a synergistic effect.

In this case, the observed actual degree of activity must be greater than the value calculated from the above formula for the expected degree of activity (E).

The invention will now be illustrated by the following examples. However, the invention is not limited to these examples only.

Example 1. Phytophthora (tomatoes) / protective test

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of an alkylaryl polyoxyethylene compound

In order to prepare the intended preparation of the active substance, 1 part by weight of the active substance or combination of active substances is mixed with the above-mentioned amount of solvent and emulsifier, and the concentrate so formed is diluted with water until the desired concentration is obtained, or a commercial preparation of the active substance or combination of active substances, diluted with water until the desired concentration is obtained.

In order to test for protective effectiveness, young plants are sprinkled with the preparation of active substance used in the prescribed dose. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Phytophthora infestans. The plants are then placed in an incubation chamber at approximately 20 ° C and 100% relative humidity.

Evaluation is performed 3 days after inoculation. Here, 0% means a degree of activity corresponding to the degree of activity of the control, while a degree of activity of 100% means that no contamination was observed.

The found effect of the active substance combination according to the invention is greater than that calculated, which means that there is a synergistic effect.

The combination of the compound of formula (I) and a halobenzimidazole of formula No. XXVII shows, at a 1: 1 ratio of the components of the mixture to each other and at a dose of 0.1 g / ha, an actual degree of activity of 73%.

The expected value for the degree of activity calculated from the Colby formula is 63% and is significantly lower.

The active substances and the experimental results are shown in the following tables.

PL 200 668 B1

Table 1

Phytophthora (tomatoes) / protective test

<td>Active substance known:</td><td>Dose of active substance in g / ha</td><td>Degree activity in%</td>

<td>Compound of formula (XXVII) Xtt&gt; H, C SO,³ \_WITH ²Ck</td><td> 0,1</td><td> 30</td>

<td>Compound of formula (I)</td><td> 0,1</td><td> 47</td>

The mixture according to the invention

<td>Substance active</td><td>Quantity ratio of the mixture components</td><td>The dose of the active substance in g / ha</td><td>The actual stppin-activity</td><td>Expected value calculated according to Colby's induction</td>

<td>Xxvii</td><td></td><td> 0,1</td><td></td><td></td>

<td> +</td><td> } 1:1</td><td> +</td><td> } 73</td><td> 63</td>

<td>AND</td><td></td><td> 0,1</td><td></td><td></td>

Table 4

Phytophthora (tomatoes) / protective test

<td>Active substance known:</td><td>Dose of active substance in g / ha</td><td>Degree activity in%</td>

<td>Compound of formula (I)</td><td> 1</td><td> 47</td>

<td>Dichlofluanid (IVa) / TA / S — cci₂f \ / &lt;^1Va&gt; ^ SO ^ CCH.,)²</td><td> 20</td><td> 5</td>

PL 200 668 B1

The mixture according to the invention

<td>Substance active</td><td>Quantity ratio of the mixture components</td><td>Dose of active substance in g / ha</td><td>The actual degree of activity</td><td>Expected value calculated according to Colby's formula</td>

<td>(AND)</td><td></td><td> 1</td><td></td><td></td>

<td> +</td><td> } 1:20</td><td> +</td><td> } 87</td><td> 50</td>

<td>dichlofluanid (IVa)</td><td></td><td> 20</td><td></td><td></td>

Table 5

Phytophthora (tomatoes) / protective test

<td></td><td colspan="2">Active substance known:</td><td></td><td>The dose of the substance</td><td>Degree</td>

<td></td><td></td><td></td><td></td><td>active in g / ha</td><td>activity in%</td>

<td colspan="2">Compound of formula (I)</td><td></td><td></td><td> 1</td><td> 47</td>

<td></td><td>^H.AND</td><td>/ CH₃</td><td></td><td></td><td></td>

<td>ij</td><td>AT</td><td>ύΜ</td><td>SOF</td><td></td><td></td>

<td></td><td></td><td>About CH₃</td><td></td><td></td><td></td>

<td>Tolilfluanid (IVb)</td><td></td><td></td><td></td><td> 20</td><td> 21</td>

<td>HjC-</td><td colspan="3">Λ-ΤΧ s — cci₂f -c ^x&gt; —N: \ = / N (CH₃)₂</td><td></td><td></td>

<td colspan="6">The mixture according to the invention</td>

<td>Substance</td><td></td><td>The ratio of</td><td>Sub- dose</td><td colspan="2">Actual Expected value</td>

<td>active</td><td></td><td>syntactic-</td><td>stand up and be active</td><td>degree of active</td><td>calculated by</td>

<td></td><td></td><td>the mixture</td><td>r ^^ as above in g / ha</td><td>natures</td><td>Colby's formula</td>

<td>(AND)</td><td></td><td></td><td> 1</td><td></td><td></td>

<td> +</td><td> }</td><td> 1:20</td><td> + }</td><td> 95</td><td> 58</td>

<td>Tolilfluanid (IVb)</td><td></td><td></td><td> 20</td><td></td><td></td>

<td></td><td></td><td></td><td>Table 8</td><td></td><td></td>

<td></td><td></td><td colspan="3">Phytophthora (tomatoes) / protective test</td><td></td>

<td></td><td colspan="2">Active substance known:</td><td></td><td>The dose of the substance</td><td>Degree</td>

<td></td><td></td><td></td><td></td><td>active in g / ha</td><td>activity in%</td>

<td colspan="2">Compound of formula (I)</td><td></td><td></td><td> 1</td><td> 47</td>

<td></td><td>^H.AND &gt;&gt;</td><td> /°^H.3</td><td></td><td></td><td></td>

<td>X j</td><td></td><td>ύΜ</td><td></td><td></td><td></td>

<td></td><td></td><td>Oh CHj</td><td></td><td></td><td></td>

<td colspan="4">Bitertanol (IIc)</td><td> 10</td><td> 4</td>

PL 200 668 B1

The mixture according to the invention

<td>Substance active</td><td>Quantity ratio of the mixture components</td><td>Dose of active substance in g / ha</td><td>The actual degree of activity</td><td>Expected value calculated according to Colby's formula</td>

<td>(AND)</td><td></td><td> 1</td><td></td><td></td>

<td> +</td><td> } 1:10</td><td> +</td><td> } 73</td><td> 49</td>

<td>Bitertanol (IIc)</td><td></td><td> 10</td><td></td><td></td>

Table 9

Phytophthora (tomatoes) / protective test

<td>Active substance known:</td><td>Dose of active substance in g / ha</td><td>Degree activity in%</td>

<td>Compound of formula (I)^H.3^C.KxCH³“ΛΑ ^ -jOCty 3</td><td> 1</td><td> 47</td>

<td>Tebuconazole (III) Cl ^ _2-CH₂-CH₂-CC (CH₃)₂ &lt;?^h2 AND about N</td><td> 10</td><td> 5</td>

The mixture according to the invention

<td>Substance active</td><td>Quantity ratio of the mixture components</td><td>Dose of active substance in g / ha</td><td>The actual degree of activity</td><td>Expected value calculated according to Colby's formula</td>

<td>(AND)</td><td></td><td> 1</td><td></td><td></td>

<td> +</td><td> } 1:10</td><td> +</td><td> } 73</td><td> 50</td>

Tebuconazole (III)

PL 200 668 B1

Table 10

Phytophthora (tomatoes) / protective test

<td>Active substance known:</td><td>Dose of active substance in g / ha</td><td>Degree activity in%</td>

<td>Compound of formula (I)</td><td> 1</td><td> 47</td>

<td>Triadimenol (IIb) OH V "O-CH-CH — C (CH₃)₃ Λ &lt;j N—^f</td><td> 10</td><td> 0</td>

<td colspan="3">The mixture according to the invention</td>

<td colspan="3">Substance Quantity ratio- Sub dose- Actual value ccekqunna active quartile component- active- soppumpkkt- calculated according to of the mixture in g / ha of the Colby formula</td>

<td colspan="3">(I) 1 +} 1:10 +} 88 47 Triadimenol (IIb) 10</td>

<td colspan="3">Table 11 Phytophthora (tomatoes) / protective test</td>

<td>Active substance known:</td><td>Dose of active substance in g / ha</td><td>Degree activity in%</td>

<td>Compound of formula (I) 3</td><td> 1</td><td> 47</td>

<td>Imidacloprid (XXII) Π Y^H.and! | -ho₂</td><td> 10</td><td> 0</td>

PL 200 668 B1

The mixture according to the invention

<td>Substance active</td><td>Quantity ratio of the mixture components</td><td>Dose of active substance in g / ha</td><td>The actual degree of activity</td><td>Expected value calculated according to Colby's formula</td>

<td>(AND)</td><td></td><td> 1</td><td></td><td></td>

<td> + }</td><td> 1:10</td><td> +</td><td> } 71</td><td> 47</td>

<td>Imidacloprid (XXII)</td><td></td><td> 10</td><td></td><td></td>

Table 12

<img file="PL200668B1_D0045.tif" />

The mixture according to the invention

<td>Substance active</td><td>Quantity ratio of the mixture components</td><td>Dose of active substance in g / ha</td><td>The actual degree of activity</td><td>Expected value calculated according to Colby's formula</td>

<td>(AND)</td><td></td><td> 1</td><td></td><td></td>

<td> +</td><td> } 1:10</td><td> +</td><td> } 62</td><td> 48</td>

(XXI) (20)

PL 200 668 B1

Table 13

Phytophthora (tomatoes) / protective test

<td>Active substance known:</td><td>Dose of active substance in g / ha</td><td>Degree activity in%</td>

<td>Compound of formula (I)</td><td> 1</td><td> 47</td>

<td>Fenhexamid (VIII) OH^CH3 eHd</td><td> 10</td><td> 13</td>

The mixture according to the invention

<td>Substance active</td><td>Quantity ratio of the mixture components</td><td>Dose of active substance in g / ha</td><td>The actual degree of activity</td><td>Expected value calculated according to Colby's formula</td>

<td>(AND)</td><td></td><td> 1</td><td></td><td></td>

<td> + }</td><td> 1:10</td><td> +</td><td> } 70</td><td> 54</td>

<td>Fenhexamid (VIII)</td><td></td><td> 10</td><td></td><td></td>

Table 14

Phytophthora (tomatoes) / protective test

<td colspan="4">Active substance known:</td><td></td><td>The dose of the substance</td><td>Degree</td>

<td></td><td></td><td></td><td></td><td></td><td>active in g / ha</td><td>activity in%</td>

<td>Compound of formula (I) CH C</td><td>^H.3^C.S.</td><td></td><td></td><td></td><td> 1</td><td> 47</td>

<td>Pj</td><td>L.</td><td>Lu</td><td>fi</td><td></td><td></td><td></td>

<td>h₃c ^ X</td><td>H.</td><td>if</td><td>Γ pp</td><td>F.</td><td></td><td></td>

<td></td><td></td><td>δ</td><td>óh₃</td><td></td><td></td><td></td>

<td>Carpropamid (V)</td><td></td><td></td><td></td><td></td><td> 10</td><td> 0</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Ml—</td><td></td><td>^ CH,</td><td>about</td><td>-Cl</td><td></td><td></td>

<td></td><td></td><td>HC</td><td></td><td></td><td></td><td></td>

PL 200 668 B1

The mixture according to the invention

<td>Substance active</td><td>Quantity ratio of the mixture components</td><td>Dose of active substance in g / ha</td><td>The actual degree of activity</td><td>Expected value calculated according to Colby's formula</td>

<td>(AND)</td><td></td><td> 1</td><td></td><td></td>

<td> +</td><td> } 1:10</td><td> +</td><td> } 90</td><td> 47</td>

<td>Carpropamid (V)</td><td></td><td> 10</td><td></td><td></td>

Table 15

Phytophthora (tomatoes) / protective test

<td>Active substance known:</td><td>Dose of active substance in g / ha</td><td>Degree activity in%</td>

<td>Compound of formula (I)</td><td> 1</td><td> 47</td>

<td>Spiroxamine (XI) (CH₃)₃C - / ^ S &lt;Ί _CJ. O ^ CH-N ^²”⁵² ^ C₃H, -n</td><td> 10</td><td> 0</td>

The mixture according to the invention

<td>Substance active</td><td>Quantity ratio of the mixture components</td><td>Dose of active substance in g / ha</td><td>The actual degree of activity</td><td>Expected value calculated according to Colby's formula</td>

<td>(AND)</td><td></td><td> 1</td><td></td><td></td>

<td> +</td><td> } 1:10</td><td> +</td><td> } 86</td><td> 47</td>

Spiroxamine (XI)

PL 200 668 B1

Table 17

Phytophthora (tomatoes) / protective test

<td>Active substance known:</td><td>Dose of active substance in g / ha</td><td>Degree activity in%</td>

<td>Compound of formula (I)</td><td> 1</td><td> 47</td>

<td>Compound of formula (XXVIII) (27) iTl jO CH, F .0. AND^{3 h}3ct 'Κ γ -ch₃ 0</td><td> 1</td><td> 9</td>

The mixture according to the invention

<td>Substance active</td><td>Quantity ratio of the mixture components</td><td>Dose of active substance in g / ha</td><td>The actual degree of activity</td><td>Expected value calculated according to Colby's formula</td>

<td>(AND)</td><td></td><td> 1</td><td></td><td></td>

<td> +</td><td> } 1:1</td><td> +</td><td> } 72</td><td> 52</td>

<td>(XXVIII) (27)</td><td></td><td> 1</td><td></td><td></td>

Table 18

Phytophthora (tomatoes) / protective test

<td>Active substance known:</td><td>Dose of active substance in g / ha</td><td>Degree activity in%</td>

<td>Compound of formula (I)^H.3^C.K ^ CH³ΑΑ ^ χΟΧ</td><td> 1</td><td> 47</td>

<td>Compound of formula (XIV) (13) | j Ν * '' '»» L. ¹ JL J1 - j^{Cl F}h αΛα.^v l]</td><td> 1</td><td> 8</td>

PL 200 668 B1

The mixture according to the invention

<td>Substance active</td><td>Quantity ratio of the mixture components</td><td>Dose of active substance in g / ha</td><td>The actual degree of activity</td><td>Expected value calculated according to Colby's formula</td>

<td>(AND)</td><td></td><td> 1</td><td></td><td></td>

<td> +</td><td> } 1:1</td><td> +</td><td> } 62</td><td> 51</td>

<td>(XIV) (13)</td><td></td><td> 1</td><td></td><td></td>

Table 19

Phytophthora (tomatoes) / protective test

<td>Active substance known:</td><td>Dose of active substance in g / ha</td><td>Degree activity in%</td>

<td>Compound of formula (I) HC. CH₃ .. ΛΜχ</td><td> 1</td><td> 56</td>

<td>Compound of formula (XXXXVIa) (40) Copper oxychloride</td><td> 50</td><td> 0</td>

The mixture according to the invention

<td>Substance active</td><td>Quantity ratio of the mixture components</td><td>Dose of active substance in g / ha</td><td>The actual degree of activity</td><td>Expected value calculated according to Colby's formula</td>

<td>(AND)</td><td></td><td> 1</td><td></td><td></td>

<td> +</td><td> } 1:50</td><td> +</td><td> } 82</td><td> 56</td>

<td>Copper oxychloride (XXXXVIa)</td><td></td><td> 50</td><td></td><td></td>

Table 20

Phytophthora (tomatoes) / protective test

<td>Active substance known:</td><td>Dose of active substance in g / ha</td><td>Degree activity in%</td>

<td>Compound of formula (I) H.₃Ck CH₃</td><td> 1</td><td> 56</td>

<td>Compound of formula (XII) (11) Azoxystrobin AND? Mii IN Ch₃</td><td> 1</td><td> 55</td>

PL 200 668 B1

The mixture according to the invention

<td>Substance active</td><td>Quantity ratio of the mixture components</td><td>Dose of active substance in g / ha</td><td>The actual degree of activity</td><td>Expected value calculated according to Colby's formula</td>

<td>Formula (I)</td><td></td><td> 1</td><td></td><td></td>

<td> + }</td><td> 1:1</td><td> +</td><td> } 95</td><td> 80</td>

<td>Azoxystrobin (XII)</td><td></td><td> 1</td><td></td><td></td>

Table 21

Phytophthora (tomatoes) / protective test

<td colspan="3">Active substance known:</td><td>Dose of active substance in g / ha</td><td>Degree activity in%</td>

<td colspan="2">Compound of formula (I)^H.3^Ck .CH, eu n ³</td><td></td><td> 1</td><td> 56</td>

<td>Pil h₃what ^ | * Λ</td><td> 3 1 ^stheir₃</td><td>cx</td><td></td><td></td>

<td colspan="2">Compound of formula (XIII) (12) Trifloxystrobin</td><td></td><td> 1</td><td> 0</td>

<td></td><td></td><td></td><td></td><td></td>

<td>\ AJi</td><td>T.</td><td></td><td></td><td></td>

<td></td><td>τΊ</td><td></td><td></td><td></td>

<td></td><td>AND Ch</td><td></td><td></td><td></td>

The mixture according to the invention

<td>Substance active</td><td>Quantity ratio of the mixture components</td><td>Dose of active substance in g / ha</td><td>The actual degree of activity</td><td>Expected value calculated according to Colby's formula</td>

<td>Formula (I)</td><td></td><td> 1</td><td></td><td></td>

<td> +</td><td> } 1:1</td><td> +</td><td> } 69</td><td> 56</td>

Trifloxystrobin